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Volcarona disguised itself as the sun as Ghetsis arrived on his Hydreigon at the chair in the throne room at N's Castle after N was defeated by Black and Reshiram. It set fire to the battlefield as Black and Ghetsis were battling. Black used Musha in a bit to see how he could defeat Ghetsis an saw a shape in the sun. He had Musha attack and exposed Volcarona. He used his Pokédex and saw that the flames came from Volcarona's ember flames and as they hit the ground, they became alight. Brav used Whirlwind to blow them away. Black's Pokémon attack Ghetsis' all at once, with Costa attacking Volcarona with Stone Edge. With Ghetsis' other Pokémon, Volcarona was defeated.
None of Volcarona's moves are known.