You are currently in Classic Mode.
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First, go to single player, choose very easy with 5 lives.
Go through and beat the game, after you defeat the master hand, this screen should appear (if you beat it under 20 minutes, you will get Captain Falcon first, see below):
You will need to fight and defeat Jigglypuff on the Saffaron City stage:
After Jigglypuff is defeated, it will be playable:
For Luigi, you need to beat the Target Test / Bonus Level 1 with all 8 original characters. The last character you beat it with will be the one you fight Luigi with. For example, I wanted to use Mario, so I saved his Target Test for last:
Then Luigi challenges you to a fight:
You will fight him on the Peach's Castle stage:
After defeated, Luigi will be playable:
To get Captain Falcon, go to single player, choose the easiest settings again, and beat the game in under 20 minutes (Easy settings will make the game quicker).
If you are able to beat it in under 20 minutes, Captain Falcon will challenge you:
You will fight him on the Brinstar stage:
Once you defeat him, he will be playable:
For Ness, go to a single player game, choose Normal Difficulty, and 3 lives:
Beat the game without continuing, and Ness will challenge you:
You will fight him on the Dream Land stage:
If you defeat him, Ness will be playable:
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