Viewtiful Joe: Red Hot Rumble

Successfully complete all 40 Trial mode missions. Then, highlight a character and press Square at the selection screen.

Complete the V-Puzzles for the Special Edition movies.

Most characters can be unlocked by completing the movie or challenge that they are featured in. Complete the indicated task to unlock the other characters.

Charles the Third: Use two different characters to complete a movie.
Dante: Complete "Riddle Of The Incan Empire".
Dark Hero Jet Black: Complete "BOSS*BOSS*BANG*BANG".
Director Blue: Complete "Atlantis: Adventures of the Four Seas Special Edition".
Fighter Bianky and Friends: Complete "Red Hot Rumble".
Gran Bruce: Use four different characters to complete a movie.
Heroine Silvia: Complete "Truth of the Black Film Special Edition".
Hulk Davidson: Use three different characters to complete a movie.
Manager Jet: Complete "Gulliver's Battles Special Edition".
Movie Fan Joe: Complete "Captain Blue Begins Special Edition".
Rachael: Complete "Les Acteurs Incroyable".
Sprocket: Complete a movie.
Stylish Alastor: Complete "Riddle of the Incan Empire Special Edition".
Young Blue Jr.: Complete "Viewtiful Cartoon World Special Edition".
Young Captain Blue: Complete "The Hidden Hideout".

Either complete all the V-Puzzles or all the Challenges.