Ash
Brock
Ash looks up to Brock as an older brother. He usually listens to what the rock trainer has to say, and rarely fights with him. Ash sometimes gets a bit annoyed/incredulous at Brock's girl-mania but it doesn't really bother him.
Brock has some respect for Ash as a trainer, but more for him as a person. I think his fatherly instinct (from looking after 10 younger siblings) comes out around Ash. That's not to say there's any sort of barrier between them though; as the only other guy in the group, Ash will often confide things to Brock and has respect for him.
Misty
Ash and Misty fight a lot, which isn't terribly surprising considering that they're both very stubborn people and the basis behind their travelling together - the fact that Ash stole, and totalled, her bike. Doesn't seem like a strong foundation for a friendship. ^_^.
But despite that, and despite that they're always shouting at each other either because of a) the bike, b) being lost or c) Ash's ability (or lack thereof) as a trainer, Misty is probably the best friend Ash has, and vice versa.
They care much for each other, but rarely show it. They're absolutely comfortable in each other's presence. Some have suggested they're really in love with each other but... I dunno. Ash has not shown any sign of liking her. And Misty did encourage Danny over Ash.
Misty really does realise that Ash has a lot of potential as a trainer, but that doesn't mean she's going to feed his ego at all. Instead, she makes it her goal to squash his ego flat, and in that actually does a lot to help Ash become a better trainer.
Pikachu
Ash's best friend besides Misty. Ash usually treats Pikachu as an equal; he talks to it and understands it. However, sometimes he does play the part of the 'overbearing master' as I think all Pokemon trainers do at times. This is shown on occasions where Ash tries to force Pikachu to fight battles too difficult for it.
However, that's just because Pikachu is Ash's best Pokemon. He wants Pikachu to be the best it can be, not only to further his own goal of being a Pokemon Master, but so that Pikachu can be happy (Pikachu loves battling) and reach its potential.
Also, because Pikachu is always with him, they're close friends and Ash prefers a victory shared with his best friend than with his other Pokemon.
Ash always wants what's best for Pikachu, and although their friendship had a rocky start, they'd both lay their lives on the line for each other. Ash never speaks down to Pikachu or treats it badly, although sometimes has unrealistic expectations of what Pikachu can and cannot do. But Pikachu always tries extra hard to make Ash proud of it.
Jessie
Ash gets really fed up with Team Rocket's melodrama and constant attempts to snatch Pikachu. They interfere with his dream of going on a smooth journey to be a Pokemon Master. He thinks of Jessie as a nuisance and a bad person who is not to be trusted.
However, Ash would put those feelings aside if Jessie were in trouble, because even if he doesn't like her, he's basically a nice person and hates to see anyone in difficulties.
James
As with Jessie, Ash gets annoyed with James' constant attempts to steal Pikachu. He has little respect for the Rocket as well, as he hates anyone who would be mean to Pokemon. But, also as with Jessie, he would have no problem putting his feelings aside to help him if he were in trouble.
Gary
Gary never misses an opportunity to insult Ash, and Ash in return can't stand his rival. From the word go, Gary's always been just that much better than Ash, and Ash would just love to one day teach him a lesson.
In the game, they were once best friends. I'm not sure that in the anime... I'll have to see what happens next. I think they part on okay terms, but I haven't seen that far yet.
His other Pokemon
Bulbasaur and Ash had a slightly prickly friendship at the start. Bulbasaur's 'trainer' gave it to Ash, and their first meeting wasn't a particularly good one. In a later episode where Ash is seperated from his Pokemon, Bulbasaur is the first to believe that Ash has abandoned them. But it later learns to trust and like him, especially after Ash risks his life for him.
Squirtle didn't trust Ash at first either, until Ash saved his life too. (Gee, does poor Ash have to injure himself before anyone will believe in him? ^_^;;) Then he willingly decided to go with him and was always happy to be his Pokemon.
Charizard, when it was Charmander, liked Ash a lot and tried to make him proud. However, when it evolved, it forgot the close bond it had with Ash, and its personality evolved along with its body. Now it's somewhat reckless and will not obey Ash at all, because it has no respect for him. So Ash very rarely uses the fire Pokemon for fear that he'll go out of control.
Ash once said that Pidgeotto was his friend, but very rarely uses it, except to blow Koffing/Weezing's smoke away. They don't seem to have any sort of a friendship really.
Meowth
Ash thinks Meowth is really annoying and doesn't trust him in the least. Meowth could say exactly the same thing about Ash.
Nurse Joy
Nurse Joy usually ends up having some sort of respect for Ash, however she's harsh/overbearing towards him in a motherly sort of way. If that makes any sense. She always berates him if he brings in an injured Pokemon (but geeze, why else would anyone go into a Pokemon Centre?) but does her best to help him out and his Pokemon, so Ash does like Joy, but not in the same way as Brock does. ^_^;;
Officer Jenny
Officer Jenny is quick to be distrustful of Ash, an outsider, but he usually wins her over by helping her beat Team Rocket. She usually recognises him as the good guy and has helped him out more than once.
Misty
Brock
Brock and Misty get on quite well, as they have to 'band together' against Ash's a) ego, b) ignorance and c) Team Rocket, when Ash is incapable of doing so himself.
Brock, surprisingly, does not go ga-ga over Misty, but treats her as a lady nonetheless (most of the time). Their friendship is relaxed. Because they both, at times, seem like Ash's 'sidekicks', they are often, together, pushed into the background somewhat.
There are also theories that Brock and Misty like one another, although it's not such a popular theory as the Ash-Misty one.
Jessie
Hell hath no fury like a woman scorned... Misty and Jessie fight like cats. ^_^. Jessie thinks of Misty as 'scrawny' and Misty of Jessie as an 'old hag'. Also, Misty's quick to help out her friend Ash when Team Rocket is attacking him, so they conflict a lot.
Misty can't stand Jessie's overbearing attitude, or ego. Jessie, for her part, hates Misty's 'goody-goody' attitude and blunt manner. The two characters are actually remarkably similar in a number of ways, but of course, they'd never say so.
But just as Ash would, Misty would be quick to help Jessie if she was in trouble. They may not like each other, but they have a grudging admiration for each other, which neither would ever admit.
James
I think Misty doesn't dislike James as much as she dislikes Jessie, and probably looks toward him as the more 'human' member of the team. However, that doesn't mean she likes or respects him at all. She hates thieves and is fed up with the constant interference from Team Rocket to their travels.
However, she'd help him out if he were in trouble... geeze, I'm sounding like a broken record. I won't say that again, really. ^_^;;
Meowth
Meowth once threatened to dye her hair purple. 'Nuff said.
Her Pokemon
Misty's good side (or bad, depending on how you look at) and motherly instinct come out around Togepi. She babies it a lot and is always looking out for it like a devoted parent.
She has respect for and cares for her other Pokemon, no particularly extraordinary friendships there. She loves water Pokemon. Ash said she was like a different person around them. Psyduck, however, is a different matter...
Psyduck is Misty's bane. It can be annoying, isn't an effective fighter and comes out of its ball without her calling it, effectively embarassing her.
Yet, even though Misty is always yelling at it (her favourite phrase is "Now *I'VE* got a headache!"), she wouldn't get rid of it for anything. You could say it's her favourite Pokemon, because she shows more emotion toward it than any other.
Pikachu
Pikachu took a real liking to Misty from the start, even when its trainer Ash didn't. ^_^;; It refused to do battle against her, and even cheered for her when she was battling Ash. This did not please our aspiring Pokemon Master. ^_^;;
Brock
Jessie
Jessie is the only woman Brock hasn't fallen for. I guess this is both because a) she hasn't shown herself to be kind or a Pokemon lover and b) she's a main character and it'd be tedious if Brock was love-struck every five seconds.
Jessie doesn't seem to dislike Brock as much as she does Ash and Misty. But Brock does become angry with her when she's mean to Pokemon.
James
James and Brock are pretty much total opposites, yet they don't really clash. One time they were both after the same pretty girl yet didn't fight for her, more like worked together/gushed together. ^_^;;
The two have worked together a couple of times and theirs seems slightly less hostile than the other Team Rocket/Ash/Misty interactions.
Meowth
Brock seems to dislike Meowth more than Ash or Misty do. I'm not sure why. I think it gets on his nerves. ^_^.
Pikachu
Pikachu loves Brock's food. That is enough. They're good friends, as such. *grins*
Nurse Joy/Officer Jenny
Brock would do anything to help a pretty lady, especially these two. He can hardly ever keep from blushing or stuttering when in the presence of either of them. But since he seems to like every Joy/Jenny just as much as, or more than the last, it couldn't really be considered as anything other than him being a typical guy. *grins*
His Pokemon
Brock's favourite Pokemon is Vulpix, which he received as a present. He likes looking after it and said he'd never force it to evolve. But the Pokemon he uses most is Geodude. Brock makes all his Pokemon's food himself, and is a good trainer. His Pokemon all try their best for him and he doesn't expect more than that.
James
Ash
I think that James is a bit jealous of Ash, because he'd like to be a Pokemon Master himself but isn't good enough. He also doesn't like him because he keeps stuffing up Team Rocket's plans, which makes him all the more determined to beat him some day.
Jessie
Jessie and James go together. They have the matching hair (pink for girl and blue for boy). The have the outfits, the motto, the personalities. They are Team Rocket. ^_^.
I'm not saying there's anything between them besides simple friendship. In fact, I don't think there is, and I think it's great that a guy and girl of such an age can be best friends. But, James and Jessie have both experessed mild romantic interest in each other. I don't think anything will come of it, but that's what fanfics are for, eh?
Basically, these two are such good friends they've been together for ages. They can finish each others' sentences, talk in unison and their names fit together as a pun. James puts up with a lot from Jessie but never seems to get angry.
Meowth
Meowth loses his temper at James sometimes, and vice versa, and the two often act like they don't like each other/find each other very annoying. But they're actually close friends and co-operate well.
His Pokemon
James likes his Pokemon. Team Rocket got caught because James stayed behind to rescue his Weepinbell/Victreebell from Cassidy and Butch's breeding centre. Also, his Koffing/Weezing is very loyal to him and obeys him even though he doesn't have any badges. He was once going to force it to evolve but changed his mind. Koffing evolved anyway, to make its master happy.
However, he doesn't usually have very much faith in his Pokemon, and because of that, it loses all the time.
Jessie
Meowth
Meowth seems to scratch her more than anyone else. But Jessie more than makes up for it with her lethal fans and mallet. ^_^. Similar to Meowth and James, Jessie and the cat actually get along very well and have a strong friendship, even if it is punctuated by a claw across the face or a black eye. ^_^;;
Her Pokemon
Jessie cares about Ekans/Arbok like James cares about his Koffing/Weezing. She's had it for a long time. She usually orders it around on screen, but the two must have some sort of friendship because Ekans/Arbok is very loyal to its trainer, even though Jessie doesn't have any badges.
But like James, because of Arbok's many failures, she's lost faith in its abilities as a Pokemon. So it will never become what it could have.
