Jessie's Wobbuffet is a Psychic-type Pokémon that joined Team Rocket not through capture, but through an accidental trade. Originally owned by a young trainer named Benny, who wanted to trade it away, Wobbuffet came into Jessie's possession during a Team Rocket scheme involving a fake trading machine. In the resulting confusion, Jessie's Lickitung was placed into a real trading device and was exchanged for Benny's Wobbuffet, much to her initial dismay. Despite her first reaction, this Wobbuffet would go on to become one of the most persistent and recognizable members of the Team Rocket trio, often considered a fourth member of the group alongside Jessie, James, and Meowth.

In terms of personality, Wobbuffet is best known for its seemingly vacant and air-headed demeanor. Its most famous trait is its habit of emerging from its Poké Ball on its own accord without any command from Jessie. This behavior, shared with other Pokémon like Misty's Psyduck, often disrupts Team Rocket's plans, causes them to fall from heights, or simply punctuates their motto with its cry. While its dopey and clumsy nature frequently irritates Jessie and Meowth, leading them to blame it for various mishaps, Wobbuffet is deeply loyal and caring. It has a strong affection for Jessie, shown when it instinctively protects her from attacks and becomes distressed when separated from her. Its loyalty is so profound that on one occasion, after falling in love and being given the chance to stay with a mate, Wobbuffet ultimately chose to return to Jessie's side, saving her from a Rhyperior using its signature move Counter.

Wobbuffet's role in the story is primarily that of comic relief and a recurring antagonist, often appearing as part of Team Rocket's failed schemes to steal Ash's Pikachu. Despite its goofy presentation, it is rarely used in direct combat, but when it is, it proves to be remarkably powerful. Its battle strategy relies solely on counterattacks; it uses Counter to deflect physical moves and Mirror Coat to return special attacks. This ability makes it a formidable defensive shield and allows it to defeat much stronger opponents, including fighting-type Pokémon and even legendary Pokémon like Articuno. Outside of battle, Wobbuffet has demonstrated a surprising range of skills, including driving vehicles, making Poké Puffs for Pokémon Showcases, and participating in elaborate disguises with its teammates.

Throughout its history in the anime, Wobbuffet has traveled with Jessie through Johto, Hoenn, Sinnoh, Kalos, and Alola. It was notably absent for most of the Black and White series, left behind at Team Rocket's headquarters on Giovanni's orders, but it returned to the team before their journey to Kalos. In Kalos, Wobbuffet became more active and competent in battle, even assisting Jessie in Pokémon Showcases, where it helped win a ribbon. A significant moment in its development occurred when a distortion in time and space temporarily devolved it into a Wynaut, though it was later restored to its proper form. Over time, the relationship between Wobbuffet and Jessie has strengthened considerably. While she often calls it useless and treats it poorly, episodes where Wobbuffet gets lost or considers leaving reveal her genuine hidden affection for it, culminating in moments of emotional relief when it chooses to stay with her. For notable abilities, beyond Counter and Mirror Coat, Wobbuffet has also been known to use Bide on rare occasions, and its defense is strong enough to withstand and deflect attacks from very powerful creatures, including Pikachu's Thunderbolt and Giratina's Shadow Ball.