According to SmashWiki, Meta Knight is supposed to be the best.
HUH? There isn't ANYTHING by that name (or at least spelling, which I can't be sure of either) in Super Smash Bros. Brawl. For all info, go to www.smashbros.com Also, there is a SmashWiki.
Hit every button on the Game Cube Controller all at once annnnnd.... NOTHING SPECIAL WILL HAPPEN! If you want to win as a specific character... THEN PRACTICE!!! You can use www.smashbros.com (The official Smash site, made by the creator of Smash Bros.) or SmashWiki for tech help. But that's all moot if you don't put in the time. Learn all the basics, shield, dodge, SMASHES, Perfect-Shield (Literally a tech), Ukemi (A VERY useful trick to get used to), PROPER recovery techniques, etc. Obviously, this all applies to every character, just the way some of them are timed/used will differ.
He attacks you with similar attacks to Master Hand. However, he is the left hand rather than the right hand and therefore spends most of the time on the left side of the screen. You can face him by either: -Doing Classic Mode on Normalin 18 minutes or less and reduce Master Hand's health by half. (I think you also can't use a Continue... I don't remember about that.) or -Doing Event Match #50 (Which you MUST do if you want to reach the last one, 51, which leads to unlocking Final Destination and a couple other things) If you want an attack LIST, then go to the SmashWiki. You can find almost everything there.
Thank SmashWiki for this: 1. Meta Knight 2. Snake 3. Wario 4. Falco 5. Diddy Kong 6. King Dedede 7. Marth 8. Mr. Game and Watch 9. Pikachu 10. Olimar 11. Ice Climbers 12. R.O.B. 13. Kirby 14. Lucario 15. Zero Suit Samus 16. Toon Link 17. Pit 18. Donkey Kong 19. Peach 20. Luigi 32. Fox 22. Wolf 23. Sonic 24. Sheik 25. Bowser 26. Zelda 27. Pokemon Trainer 28. Ike 29. Lucas 30. Mario 31. Ness 32. Yoshi 33. Samus 34. Jigglypuff 35. Captain Falcon 36. Link 37. Ganondorf I know. The list is surprising.
If you had checked the Super Smash Bros. Brawl Website you'd know. But, not everyone knows about that site. I'd recommend checking it for lots of good info on stuff in Brawl. (It IS made by the CREATOR of Smash Bros., so it's QUITE accurate.) www.smashbros.com Also, for other info and such, you can go to the SmashWiki. Anyway, as to how to do it: Thee are three ways: 1: To start a match as Zero Suit Samus, select Samus as your character. Then, hold shield until you are at the Stage Select Screen. You will see that where it shows the playing characters faces, it shows Z-Sut instead of Power Suit. You will then start the match will the Power Suit breaking off. (You can pick up and throw the three remaining pieces of Power Suit) 2: During a match, if you get the Smash Ball as Power Suit Samus, when you use it, you will fire the Zero Laser. This does great damage and massive drag, often resulting in easy KO's when used correctly. As a final effect, force from the shot is so great it destroys the Power Suit, and falls off, revealing Samus in her Zero Suit. (You can pick up and throw the three remaining pieces of Power Suit) WARNING: You are VERY vulnerable right after the transformation, so be ready for revenge attacks during that time. 3: During a match, you can "simply" drop the Power Suit, by doing her "secret taunt" (The Star Fox characters and Snake have Smash Taunts, which work only on their own fields, and are done differently from Samus' secret taunt). To do this, you hit the taunt buttons for Up, Down, Up really fast, in that order (Can be rather hard on the Classic and GameCube controls. Often, you'll mess up and trigger a side taunt, which stops the combo. To get used to the idea, I recommend praciticing it with the Wii-mote+Nunchuk setup first. This means you hit 1, 2, 1 to do it.) If done correctly (and is rather hard at first, so don't despair), then you will suddenly become Impervious, glow like after the Zero Laser, and drop the Power Suit (Which again, leaves three throwable pieces). WARNING: You are VERY vulnerable right after the transformation, so be ready for revenge attacks during that time. 4?: Yeah, I said three, but you can also play as Z-Suit in the Adventure mode. Any time that you get a player select that is just a box showing the characters to choose from, and if Samus is on there, you can just hit the C-stick to change back and forth of which form you wish to be. This applies to Zelda/Shiek and Pokemon Trainer's Pokemon as well.)