(BTW gonna be lots of stuff here that's already been brought up)
Also, going with the 5 companies and 8 characters option, to afford some villain representation.
Nintendo
-Mario
-Link
-Samus
-Pikachu
-Kirby
-Fox
-Bowser
-Ganondorf
Capcom
-Megaman
-Ryu
-Dante
-Arthur
-Zero
-Dr. Wily (in a modified form of his MM Soccer suit)
-M. Bison
SNK (yeah, sorry for the dominance of KoF here)
-Terry Bogard
-Kyo Kusanagi
-Haohmaru
-Marco Rossi
-Athena
-Ryo Sakazaki
-Rugal Bernstein
-Amakusa
Konami
-Simon Belmont (with various bits and bobs cannibalized from other Belmonts)
-Solid Snake
-Alucard
-Bombeyman
-Goemon
-Pentaro (hi, requisite out-of-left-field callback character)
-Dracula
-Revolver Ocelot
SEGA
-Sonic
-Akira Yuki
-NiGHTS
-Alex Kidd
-Temjin (Virtual On)
-Toejam and Earl (dual character a la Ice Climbers)
-Shadow the Hedgehog
-Dr. Robotnik
It's hard to decide so I've done it both ways:
Sega
Sonic the Hedgehog (Classic, Modern, Boom, Super Sonic recolour)
Jacky Brent [from Virtua Fighter] (Current, Model 1 [VF1], Model 2 [VF2], Model 3 [VF3])
Joe Musashi (Current, Shinobi, Revenge of Shinobi/Shinobi 3, Hotsuma)
Blaze Fielding [from Streets of Rage]
Namco
Klonoa
Dr. Don and Dr. Dan [from Point Blank]
Heihachi [from Tekken]
Jack Slate [from Dead to Rights] (Max Payne exipy)
Capcom
Mega Man (Original, X, Legends, Battle Network)
Mike Haggar [from Final Fight] (Original, Final Fight 3, Mayor outfit, Slam Masters style)
Nathan Spencer [from Bionic Commando] (Original, 2009, Rearmed, Super Joe from the arcade version)
M. Bison [from various Street Fighter games] (Original, Alpha 2, Movie, Shin Bison)
Konami
Solid Snake [from Metal Gear Solid]
Richter Belmont [from Castlevania: Rondo of Blood] (Simon Belmont recolour, Juste Belmont recolour, Trevor Belmont recolour, Leon Belmont recolour)
Sparkster [from Rocket Knight Adventures] (Original, Sparkster, Rocket Knight, Axel recolour)
Gillian Seed [from Snatcher]
Ubisoft
Rayman (Classic, Origins/Legends, Prototype)
Aveline [from Assassin's Creed III: Liberation]
Sam Fisher [from Splinter Cell] (Classic, Blacklist, Double Agent, Conviction)
Rex Power Colt [from Far Cry 3: Blood Dragon] (Default, Spandex, Godfrey Ho styled Ninja, other 80s style look here)
Warner Bros.
Batman [well he appeared in various games...] (Current look, TAS, Adam West, Year One)
Scorpion [from Mortal Kombat] (MK9 look, Classic as in the digitized fighter look, Injustice look, Sub-Zero recolour)
WayForward (not much choice...)
Shantae
Patricia Wagon [from Mighty Switch Force] (Police officer, Firewoman, bikini, Luna from Mighty Milky Way)
Console exclusives:
Nintendo
Mario (Fire Mario, Luigi recolour, Wario recolour, Waluigi recolour)
Donkey Kong
Fox McCloud [from Star Fox] (Original, Current, James McCloud, Falco)
Captain Falcon [from F-Zero]
Sony
Nathan Drake [from Uncharted]
Ratchet & Clank
Sly Cooper (Classic, Thieves in Time, Movie)
Gabe Logan [from Syphon Filter] (Sony forgot about him on PlayStation All-Stars)
Would have put Crash for the Sony one except that they don't own him so had to resort to another PS1 character.
Microsoft
Master Chief [from Halo]
Banjo-Kazooie (Original, Nuts and Bolts)
Joanna Dark [from Perfect Dark] (Original, Zero, Tuxedo [to reference GoldenEye], Kameo style [to reference the other 360 early title by Rare])
Blinx [from Blinx: The Time Sweeper] (presumably they have the rights to this game?)
Had ideas for a Rockstar roster (including Phil Collins) and a joke EA one however it is over the 10 company limit. Also with the 5 company/8 character alternative decided to choose a multiplatform angle (since having the 3 console companies and PC would limit the other companies):
Sega (too hard to decide...)
Sonic the Hedgehog
Dr. Robotnik/Eggman
Jacky Brent [from Virtua Fighter]
Joe Musashi [from Shinobi]
Blaze Fielding [from Streets of Rage]
Robo and Mobo [from Bonanza Bros.]
Beat [from Jet Set Radioooooooooooooo]
Vyse [from Skies of Arcadia]
Capcom (not easy)
Mega Man
Dr. Wily
Mike Haggar [from Final Fight]
Nathan Spencer [from Bionic Commando]
M. Bison [from various Street Fighter games]
Frank West [from Dead Rising]
Lord Raptor [from Darkstalkers]
Jill Valentine [from Resident Evil]
Namco
Klonoa
Dr. Don and Dr. Dan [from Point Blank]
Heihachi [from Tekken]
Jack Slate [from Dead to Rights] (Max Payne exipy)
Bravoman
Reiko Nagase [from Ridge Racer Type 4/64]
Nightmare [from Soul Calibur]
Dweeb [from The Outfoxies]
Konami
Solid Snake [from Metal Gear Solid]
Richter Belmont [from Castlevania: Rondo of Blood]
Sparkster [from Rocket Knight Adventures]
Gillian Seed [from Snatcher]
Cormano [from Sunset Riders]
Male and female characters [from Bishi Bashi Special] (I don't think that they have names, blue hair man and blonde woman)
Goemon
Dingo Egret/Jehuty [from Zone of the Enders: The 2nd Runner]
Square-Enix (Europe and Taito mostly)
Agent 47 [from Hitman]
Lara Croft [from Tomb Raider]
Wei Shen [from Sleeping Dogs]
Adam Jensen [from Deus Ex: Human Revolution]
Bub and Bob [from Bubble Bobble/Puzzle Bobble]
Sonic Blast Man
Black Lotus [from Bushido Blade]
A Final Fantasy character here [not into RPGs sadly to choose a character]
Nintendo
Mario (with an alternate Luigi costume, complete with unique voices! Wow!)
Link
Pikachu or Pokemon Trainer (like the one in Brawl)
Kirby
Sega
Sonic (with an alternate Shadow costume complete with etc who cares)
AiAi (I don't really know honestly)
Gilius Thunderhead
General Winter
Valve
Gordon Freeman
Chell
Heavy
Pudge
Sony
Kratos
Cole Macgrath (player would have the option of selecting from good or evil Cole)
Sackboy
Toro Inoue (if this game got a Japanese release at least; Kuro costume included)
Microsoft
Master Chief
Someone from Gears of War
Generic shooting man #3
Generic shooting man #4
Capcom
Zero (you know as well as I do that they don't care about Megaman)
Ryu
Dante
Morrigan
Namco
Pac-Man
Klonoa
Heihachi
Lloyd Irving (he's really the only Tales characters I've heard of and I know nothing about the series)
Other companies I didn't feel like sorting through
Someone from Elder Scrolls
Isaac Clarke
Big Daddy
Rayman
Solid Snake
Raiden
I can't think of anything else at the moment.
Maybe it would be like SSB where the more popular a franchise is, the more characters from said franchise would be added. In this case, just replace franchise with company. That's actually how I'm going to justify being lazy.
Nintendo
Wario
Starman (from Earthbound, not Mario)
Haunter
Shy Guy (with all the roles they can fill he'd actually be a decent fighter)
Sega
Gilius Thunderhead
Fuck I don't care about any others really
Valve
Scout
Mogul Khan
Rrrrrrrrrrrubick
Hunter
Sony
Cole Macgrath (player would have the option of selecting from good or evil Cole)
Toro Inoue (with a Kuro costume)
R Suzuki
I keep thinking of Dokodemo Issyo and I'm having a hard time thinking of other Sony series I like
Microsoft
Hahahahaha
Capcom
Megaman
Dan Hibiki
Captain Blue
lolrust (not technically a company but whatever)
Sabitsuki
Kaibutsu
Kikiyama (same as above)
Monoko
Okay I'm tired there's more I want to add here but I need some sleep. Actually I'm fucking hungry and I've got veal parmesan in my freezer so I'm gonna go eat that.
I'm lazy and tired and hungry. Goodbye.
Maaaaan, it's so hard to choose.
Nintendo
Mario
Kirby
Donkey Kong
Link
Pit
Samus Aran
Olimar
Sony Computer Entertainment
Sly Cooper
Jak and Daxter*
Ratchet and Clank*
Crash Bandicoot (not sure if this should count)
Spyro the Dragon (or this)
Spike [Ape Escape]
Parappa the Rapper
SEGA
Sonic the Hedgehog
AiAi [Super Monkey Ball]
Billy Hatcher
Alex Kidd
NiGHTS
Ristar
ToeJam and Earl*
Gunstar Red [Gunstar Heroes]
Konami/Hudson Soft
Bomberman
Simon Belmont [Castlevania]
Solid Snake [Metal Gear]
Bonk
Master Higgins [Adventure Island]
Goemon [Mystical Ninja]
Capcom
Mega Man
Mega Man X
Ryu [Street Fighter]
Phoenix Wright [Ace Attorney]
Amaterasu [Okami]
Arthur [Ghosts & Goblins]
Dante [Devil May Cry]
* - Dual character, like the Ice Climbers
Nintendo
Mr. Game & Watch
Stanley the Bugman [Donkey Kong 3]
Mallo [Pushmo]
Dillon
Lip [Panel de Pon]
Hawk [Pilotwings]
Muddy Mole [Mole Mania]
Namco-Bandai
Pac-Man
Ms. Pac-Man
Klonoa
Mr. Driller
Bravoman
Mappy
Wayforward Technologies
Shantae
Patricia Wagon [Mighty Switch Force]
Alta [Mighty Flip Champs]
Luna [Mighty Milky Way]
Konami/Hudson Soft
Penta [Penguin Adventure]
Milon [Milon's Secret Castle]
Sir Cucumber [Princess Tomato in the Salad Kingdom]
Twinbee
Vic Viper [Gradius] (sure, why not?)
Capcom
Mega Man Volnutt [Mega Man Legends]
Viewtiful Joe
Sissel [Ghost Trick]
Zack and Wiki*