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In Black, Black 2, White, and White 2, you can catch one in the Relic Castle.
Also, in Black and White, if you hatch the Egg you receive from a Trainer on Route 18, you will receive a Larvesta, which evolves at level 59 into Volcarona.
In X and Y, Larvesta can be found in a Fire type Friend Safari.
In Omega Ruby and Alpha Sapphire, Larvesta can be found in the Mirage Forest north of Route 111, as well as on the Mirage Island north of Route 113.