Jessie obtained Wobbuffet in the episode Tricks of the Trade after accidentally trading her Lickitung for him, with Wobbuffet's previous trainer, a boy named Benny who had trained Wobbuffet hard but wanted to try training a new Pokémon.
Even though Jessie often seemed annoyed with Wobbuffet, she was shown to truly care for it. This is showcased in a handful of episodes, including Who What When Where Wynaut, in which Wobbuffet temporarily went missing. Jessie was very worried and desperately went searching for him on the island. Another instance was in Dealing With a Fierce Double Ditto Drama! where Jessie was upset at James's idea to send Wobbuffet to Giovanni since they couldn't tell him apart from Narissa's Ditto. Wobbuffet also seems to care for her deeply, although his loyalty has sometimes been in question, such as in Fear Factor Phony, Wobbuffet ran away from the group after the fake ghost made by some Ghost Pokémon scared him off. While he was running scared, he saw a Kirlia dancing and fell in love with it. When Team Rocket caught Pikachu and Kirlia, Wobbuffet jumped into the mecha after it and broke the Kirlia and its Psychic Pokémon friends free from Team Rocket's capture. Entirely thanks to Wobbuffet, Team Rocket's operation was completely ruined.
Episodes primarily featuring Wobbuffet are Wobbu-Palooza, in which Ash, his friends, and Team Rocket came across a festival honoring Wobbuffet and Jessie's Wobbuffet saved the day, and The Wayward Wobbuffet, in which Wobbuffet became separated from Jessie and went on an action-packed adventure.
Following the Team Rocket trio's journey in Sinnoh, Jessie was forced to leave Wobbuffet at Team Rocket's headquarters as he is not a Pokémon native in the Unova region and would attract attention.
Wobbuffet was used occasionally for battles. Wobbuffet's knowledge of moves like Counter and Mirror Coat came in handy, since Team Rocket often found itself on the receiving end of powerful attacks.
Wobbuffet usually served as a comic relief character. It would emerge from its Poké Ball frequently and often at inappropriate times. Since the episode Tunnel Vision, Wobbuffet had his place in the Team Rocket motto, first before Meowth (which usually left him very upset) and some episodes later, right after Meowth. It could often be heard crying out subsequent to the "Team Rocket is blasting off again!" line, even if it was not out of its Poké Ball when the team was sent blasting off. Wobbuffet was thus somewhat a fourth team member.
Team Rocket have also had various vehicles and robots based on it.