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Broly is never in an episode of DBZ, he is in 3 of the Dragon Ball Z movies.
broly
you have o play though the scenarios an till you unlock the z items Son of Paragas + Hatred of Goku and then you fusion them
Dragon Ball Z: Broly - The Legendary Super Saiyan, a page on Dragon Ball Wiki, has a list of the music near the bottom of the page under the section called Music.
lssj3 broly