The moment she saw Buneary in the episode Setting The World On Its Buneary, she was determined to catch her due her cuteness, but failed due her lack of knowledge. At the end Buneary expressed its crush towards Ash's Pikachu with her strange behavior towards him. Dawn managed the catch the Pokémon and Buneary was more than willing to go knowing she would travel with Pikachu by her side. This caused a Phione to fight against Pikachu, but Buneary decided to fight Phione. Phione was defeated and returned to its family.
Ever since then, Dawn's Buneary was used a lot in the Pokémon Contests as well as in battle. As time went on, Buneary appeared to lose her romantic feelings for Pikachu. Despite her small size, Buneary was surprisingly powerful and was often used in battle as well as in contests.
Buneary had a big crush on Ash's Pikachu. Later, despite going separate ways with their respective trainers, when Pikachu and Buneary were reunited in East Unova, Buneary was shown still interested in Pikachu.
Buneary and Ambipom are the only Pokémon of Dawn's who haven't disobeyed her. Coincidentally, they are both Normal types.
When Buneary gets near Pikachu, she swishes her fluff on her legs as if it was a skirt.
Buneary is Dawn's first Pokémon to be confirmed female.