You can get Volcarona by catching it at Relic Castle or making your Larvesta (if you have one) evolve into Volcarona starting from level 59.
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volcarona may not be considered to be a legendary as it does infact evolve from a Pokemon called larvesta, but the Pokemon volcarona is considered to be a legendary Pokemon.
In relic castle
Larvesta evolves into Volcarona.
You can catch the main white legendary, Kyrugem, Virizion, Cobalion, Terrakion, Thunderous, Victini, Zorua, Zoroark, Volcarona, and Landorus.
You get a Larvesta which evolves into a Volcarona