From the Super Mario Wiki, the Mario encyclopedia
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Poké Balls are important items originating from the Pokémon series; their purpose is to store and mobilize Pokémon within the ball when they are not in battle. They have appeared in all six installments of the Super Smash Bros. series as items, and serve as the Pokémon series emblem. When thrown, the Poké Ball releases a random Pokémon out of the ball, which says its cry and attacks or moves around. In Super Smash Bros. Brawl and Super Smash Bros. Ultimate, the Pokémon Trainer uses a Poké Ball to change between his three different Pokémon: Charizard, Squirtle and Ivysaur.
In Super Smash Bros. for Nintendo 3DS / Wii U and Super Smash Bros. Ultimate, the Master Ball variant of Poké Ball appears as an item. They specifically release only rare and Legendary Pokémon, while the regular Poké Ball can release any Pokémon.
For a complete listing of Pokémon coming out of Poké Balls, see the Pokémon article.
Super Smash Bros. Melee
Super Smash Bros. Brawl
Super Smash Bros. for Nintendo 3DS / Wii U
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