XY063/Plot

,, and are traveling to Lumiose City to prepare for Ash's Gym  against. Elsewhere, Clemont's Bunnelby defeats his in a practice battle against Clembot. After the battle, Clemont compliments Bunnelby on mastering and then decides to program Ash's battling style into Clembot so that their practice sessions will be even more realistic.

As Ash is thinking about his upcoming match against Clemont, he is interrupted by a from Jessie's Pumpkaboo. approaches, as usual, preparing for a fresh attempt at stealing. However, they are defeated easily by just one from Pikachu. During their blast-off, Jessie and are separated from James,, and Pumpkaboo. The latter three notice Jessie's absence and quickly begin their search for her, while Jessie and Wobbuffet search for them as well. During their search, however, Jessie and Wobbuffet are attacked by a wild and fall over a cliff into the water. They are rescued by a man named Dr. White, who gives Jessie a Cheri Berry and leads her back to his home so she can change into something dry.

While Jessie worries whether her new outfit looks good on her, she watches Wobbuffet get along happily with Dr. White's and, noticing as she does so how Dr. White has a great number of berries growing in his garden. While the doctor tells Jessie how he is an amateur when it comes to gardening, a man and his come by to deliver some fertilizer for the berries. In gratitude for his saving her life, Jessie accompanies the doctor on his house calls, assisting him in whatever ways she can. While visiting Beatrice and healing her, White and Jessie hear about a who has been setting traps in the area. During their house calls, Jessie proves to be very adept at holding down a flailing so the doctor can treat it. While helping Dr. White, Jessie finds herself captivated by him and wonders whether she should stay with him and live for happiness and love rather than for evil.

Meanwhile, while Serena, Bonnie, and Ash are having lunch, wanders off and is drawn into a trap laid by the Pokémon hunter mentioned before. The trap severely injures Dedenne, so after freeing it, the group hurries to Dr. White's clinic. Dr. White siphons the excess electricity and Dedenne recovers, much to the group's relief. Although Jessie tries to hide her true identity from Ash and, they discover that she is at the clinic acting as Dr. White's assistant. As the group agrees to keep her membership in Team Rocket a secret from Dr. White, James and Meowth overhear her admitting to them that she has decided to quit Team Rocket and stay with White instead. At first, Meowth wants to go talk to Jessie, but James holds him back, saying that they should not interfere with what Jessie wants, and so they leave sadly.

While the group is staying at Dr. White's clinic, James arrives there, thoroughly beaten up, and begs for help from Ash, Serena, and Bonnie. He tells them how Meowth,, and Pumpkaboo have been captured by a Pokémon hunter, but he is reluctant to ask for Jessie's assistance. Ash, Serena, and Bonnie agree to go help James, and they distract the Pokémon hunter while James sneaks in from behind and tries to free the three Pokémon. When Jessie hears that Meowth, Inkay, and Pumpkaboo have been captured by a Pokémon hunter, she witnesses Dr. White running for Beatrice and reassuring himself that she is all right, hearing him say how Beatrice means so much to him and he was worried that she might have done something stupid. Realizing that White was never in love with her, Jessie leaves Wobbuffet behind with his new friends and goes to rescue James and the others from the Pokémon hunter. Rejoining Team Rocket, she begins to help fight the Pokémon hunter, when Wobbuffet appears to battle the hunter's. Jessie realizes that Wobbuffet would rather be with her than at Dr. White's clinic, and working together with Ash and company, Team Rocket defeats the Pokémon hunter and continues onward, with Jessie realizing that she has the best friends in the world in her life with Team Rocket.

Meanwhile, back at the Lumiose Gym, Clemont finishes programming the data about Ash into Clembot, but Clembot cannot comprehend all the new data and explodes.