All the characters in Sonic All Stars Transformed are unlocked by completing all levels of the game. Some characters require certain goals like race points but most of these are automatically achieved upon completing the game.
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Sonic Underground is an animated TV series. And no, you cannot unlock episodes, or characters other than Sonic, from Sonic Underground in Super Smash Bros Brawl.
Sorry, but there is no character as 'super sonic' in the game ultimate flash sonic, the only unlock-able characters are Amy Rose and Shadow The Hedgehog. For all the unlocked characters+all cheats+the full Juke box type in the password 595313131313131.
To unlock him, the player must find the Sonic Tokens in the Resort Island course, finish the race in at least 3rd place, and then beat him in a one-on-one race against him.