Brock had a Vulpix that he obtained from Suzy in Kanto in Pokémon Fashion Flash.
Vulpix was given to Brock by Suzy in the episode Pokémon Fashion Flash. Suzy was Brock's idol, and Vulpix took a liking to him, which was surprising, as the little Pokémon had a very snobbish nature. It even liked Brock's homemade Pokémon food. It drove away Team Rocket with a very powerful Fire Spin, driving home the point that a focus on outer beauty could eclipse a Pokémon's inner strength. Impressed with the way Brock cared for his Geodude and Ash's Pikachu, Suzy decided that Brock might be able to take better care of Vulpix than she could.
Like many of Brock's Pokémon, Vulpix received very little screen time compared to the Pokémon of other main characters. When it was featured, Brock was often seen grooming and pampering it. This led to events in The Ninja Poké-Showdown, where Misty offered to trade her Psyduck for Vulpix, being sick of her Psyduck's headache and annoyed at Brock's compliments of Vulpix. Later the group met the Eevee brothers in The Battling Eevee Brothers who were throwing an evolution party for their younger brother Mikey to evolve his Eevee. Pyro of the Eevee Brothers offered Brock a Fire Stone to evolve Vulpix. However, Brock declined, saying that he didn't want to force Vulpix to evolve if it didn't want to.
Brock later met up with Suzy again in Johto and returned Vulpix to her in Beauty and the Breeder, saying at the time that he had always felt that Vulpix wasn't really his and he was just looking after it for a time. It also reappeared in a flashback in Gotta Catch Ya Later!.
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