Alternate costumes
Successfully complete all V-Puzzles to unlock the "EX Color" option at the character selection screen. Highlight a character and press X to choose the EX version of their costume.

Anime Concept Art
Successfully complete the indicated Story mode chapter to unlock the corresponding artwork:

Concept Art 1: Jadow Stars: V-Puzzle 7
Concept Art 2: Jadow Villains: V-Puzzle 8
Concept Art 3: Gedow Stars: V-Puzzle 9
Concept Art 4: Gedow Villains: V-Puzzle 10
Concept Art 5: Main Villains: V-Puzzle 11
Concept Art 6: Main Stars: V-Puzzle 12

Movies
Successfully complete the indicated Story mode chapter to unlock the corresponding movie:

Atlantis: Four Adventures Of The Sea Special Edition: V-Puzzle 6
Atlantis: Four Adventures Of The Sea: Gulliver's Battles
Boss*Boss*Bang*Bang: All previous chapters except The Hidden Hideout
Ending Movie: Les Acteurs Incroyable
Captain Blue Begins: Viewtiful Cartoon World
Captain Blue Begins Special Edition: V-Puzzle 3
Gulliver's Battles: Truth Of The Black Film
Gulliver's Battles Special Edition: V-Puzzle 5
Les Acteurs Incroyable: Atlantis: Four Adventures Of The Sea
Red Hot Rumble: Boss*Boss*Bang*Bang
Riddle Of The Incan Empire! Special Edition: V-Puzzle 1
The Hidden Hideout: Any chapter with Charles The Third, Hulk Davidson, and Gran Bruce
Truth Of The Black Film: Captain Blue Begins
Truth Of The Black Film Special Edition: V-Puzzle 4
Viewtiful Cartoon World Special Edition: V-Puzzle 2
Viewtiful Cartoon World: Riddle Of The Incan Empire!
Opening Movie: Riddle Of The Incan Empire!
Last Battle Intro Movie: Les Acteurs Incroyable

Play as Charles The Third
Successfully complete any Story mode chapter with any two characters to unlock Charles The Third.

Play as Dark Hero Jet Black
Successfully complete the Boss*Boss*Bang*Bang chapter in Story mode to unlock Dark Hero Jet Black.

Play as Director Blue
Successfully complete the Gulliver's Battles Special Edition chapter in Story mode to unlock Director Blue.

Play as Fighter Bianky and Friends
Successfully complete the Red Hot Rumble chapter in Story mode to unlock Fighter Bianky and Friends.

Play as Gran Bruce
Successfully complete any chapter in Story mode with any four characters to unlock Gran Bruce.

Play as Heroine Silvia
Successfully complete the Viewtiful Cartoon World Special Edition chapter in Story mode to unlock Heroine Silvia.

Play as Hulk Davidson
Successfully complete any chapter in Story mode with any three characters to unlock Hulk Davidson.

Play as Manager Jet
Successfully complete the Atlantis: Four Adventures Of The Sea Special Edition chapter in Story mode to unlock Manager Jet.

Play as Movie Fan Joe
Successfully complete the Captain Blue Begins Special Edition chapter in Story mode to unlock Movie Fan Joe.

Play as Rachel
Successfully complete the Les Acteurs Incroyable chapter in Story mode to unlock Rachel.

Play as Sprocket
Successfully complete any chapter in Story mode with any character to unlock Sprocket.

Play as Stylish Alastor
Successfully complete the Riddle Of The Incan Empire! Special Edition chapter in Story mode to unlock Stylish Alastor.

Play as Young Blue Jr.
Successfully complete the Truth Of The Black Film Special Edition chapter in Story mode to unlock Young Blue Jr..

Play as Young Captain Blue
Successfully complete The Hidden Hideout chapter in Story mode to unlock Young Captain Blue.