The Poké Ball (Japanese: モンスターボール, Monsutābōru, Monster Ball) is an item that, if thrown, will release one of a number of Pokémon. The Pokémon do a number of things, including attack one's opponent, change the properties of the stage, and induce status effects. The Poké Balls in Super Smash Bros. release Pokémon from Pokémon Red/Blue/Yellow, while the Poké Balls in Super Smash Bros. Melee release Pokemon from Pokémon Gold/Silver/Crystal. The appearance of Groudon in Super Smash Bros. Brawl confirms that Brawl will have Pokémon from Ruby/Sapphire/Emerald, and Piplup confirms Diamond and Pearl Pokémon.
If you go into Training Mode and use a Poké Ball, whatever Pokémon comes out of it will come out of the next Poké Ball thrown in Melee mode.