Dawn's Buneary was first encountered wild on Route 202, immediately demonstrating a persistent affection for Ash's Pikachu. It often acted shyly around Pikachu, covering its face with its fur when flustered, contrasting its confident battling style against other Pokémon.
Dawn captured Buneary after multiple attempts. An initial battle using Piplup ended in failure when Buneary defeated Piplup with Dizzy Punch and Bounce. Later, trapped by Team Rocket alongside Pikachu, the two worked together to escape. Dawn then rematched Buneary; Piplup successfully countered its moves, enabling her official capture.
As a primary contest Pokémon for Dawn, Buneary competed in numerous Sinnoh Pokémon Contests. Its debut was in the Jubilife City Contest, advancing to the semifinals before losing to Zoey's Glameow. Buneary used Ice Beam to freeze the stage, but Zoey strategically broke the ice for an advantage. Buneary later won the Hearthome Collection fashion event, performing Ice Beam-enhanced acrobatics in a snow-themed outfit. It also contributed to Dawn's Daybreak Town Contest victory via a coordinated Double Performance with Piplup, creating frozen Bubble Beams.
Buneary faced challenges linked to Dawn's past trauma. During the Daybreak Town Contest finals, Ursula exploited Dawn's childhood fear of Plusle and Minun by having her Pokémon shock Buneary and Piplup. Though initially overwhelmed, Buneary and its teammates helped Dawn overcome this fear.
Buneary was integral to developing Dawn's contest combinations. It participated in creating the "Flame Ice" technique, combining Mamoswine's Ice Shard with Cyndaquil's Flame Wheel. Later, Buneary helped refine the "Ice Chandelier" combination, using Ice Beam alongside Pachirisu's Discharge, though the technique was ultimately perfected using Buneary and its Ice Beam.
In non-contest battles, Buneary fought in the Hearthome City Tag Battle Competition alongside Conway's Slowking, reaching the finals. It battled Maylene's Meditite at the Veilstone Gym but was defeated despite utilizing agility and Bounce. A notable interaction saw a wild Phione fall in love with Buneary, leading to a battle Buneary won using Bounce.
Biologically, Buneary's distinctive rolled ears functioned as defensive mechanisms and powerful offensive weapons. It could extend them forcefully to shatter boulders or slam opponents hard enough to make adults cry. Its ears also enabled high jumps by striking the ground. The species typically sleeps with its head tucked into its fur for warmth, and the position of its ears reflects its health state, with both rolled indicating distress.
In the manga *Pocket Monsters Diamond & Pearl* by Sakai Takayuki, Buneary appears under Dawn's ownership but does not participate in contests, as this adaptation reimagines Dawn solely as a Pokémon Trainer.