Dawn's Buneary is the first Pokemon caught by Dawn. She debuts in Setting the World on its Buneary.
Buneary first appears as she saves Ash's Pikachu from being hit by Officer Jenny and runs away when she sees Dawn. She then sneaks off with Pikachu and the two are grabbed by Team Rocket who is planning on taking them both to the boss, but they are saved by Dawn and Ash and Buneary allows herself to be caught by Dawn. She is a target to Team Rocket who tries to capture her and the gang's other Pokemon several times.
Buneary seems to have a romantic crush on Ash's Pikachu and tries to impress him. She also cares about her trainer very much.