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#48 "Holy Matrimony!"
Ash and his friends see a 'missing' poster with a person who looks like a younger James. A butler comes up to them, thinking they know something about the missing child, and takes them to a huuuge house. This is James' home... he was supremely rich. James' parents have died, and in their will they said if he marries his fiance, he can get his inheritance. Meanwhile, Team Rocket - with an unwilling James - have followed them, hoping to use James to cash in on this fortune. James truly does not want to go anywhere near the house. Ash-tachi stick up for James but Jessie and Meowth are stubborn and money-hungry.
However, James' parents are not dead. They just wanted to get their son to come and marry his fiance so they could continue the family line. James' fiance is a beautiful woman who looks a lot like Jessie - named Jessiebell. Jessiebell attacks James (literally) and uses a Vileplume, trying to get him to do what she wants, while Team Ash and Rocket have been thrown outside. James is saved by a Growlithe who carries him away.
James explains to everyone how he ran away from home in the first place to escape Jessiebell; he hated rich life and especially her, because he was never refined enough and she was always trying to change him, put rules on how to behave. Growly, his Growlithe, was his only friend. Jessiebell comes back and attacks, but Growlithe and Pikachu team up to beat her Vileplume and send her running away. James goes back with Jessie and Meowth, leaving Growly behind to take care of his family. I guess he does care about them despite everything. He may not be rich now, but he has freedom which is most important.