the palm-top tiger
Hm...It's been a while since I've watched D/P, as I've been trying to catch up with B/W, but here goes.
Like most have said, Chimchar/Monferno/Infernape's moments in the D&P series were good. How Ash tried to calm it down, and how he took a lot of hits, just to see his little Chimchar be alright..it proves that Ash does care.
Paul was a good rival too. He wasn't like that bigmouth Gary, or like the rushy Barry. He was just there. Usually quiet, observant and strong, training his Pokemon to their limits. His team is among one of the best in my opinion, too. I also like how throughout the duration of the D/P saga, Paul quietly grew to be a bit more light hearted. He became nicer as the season went on.