Single Battle mode characters
Have a saved game file from Bleach: Heat The Soul 5 on your Memory Stick Duo and select the "Convert" option at the "Appendix" menu. Then, press L or R at the character selection screen in Single Battle mode to access the unlocked characters.

Characters
Complete the indicated task to unlock the corresponding character.

Aaroniero and Smart Espada: Beat Tag Master #13.
Adult Nel: Get 50,000 points in Tag Master mode.
Aizen: Beat Tag Master #18.
Bankai Ichigo's Inner Hollow: Beat Tag Master #11.
Chad with devil's left arm: Beat Tag Master #7.
Cirruci Thunderwitch: Beat Tag Master#10.
Diamond Dust Rebeliion Guy: Beat Tag Master #17.
Espada #5: Beat Tag Master #14.
Hollow Ichigo: Defeat Ichigo and Hollow Ichigo in Tag Master mode.
Kuchiki Byakuya (Bankai): Defeat him and Rukia in Tag Master mode.
Kuchiki Rukia (Shinigami form): Defeat her and Byakuya in Tag Master mode.
Madarame Ikkaku: Defeat Ikkaku/Kempachi in Tag Master mode.
Pantera Grimmjow: Complete Story mode.
Seele Schneider Ishida: Beat Tag Master #8.
Senna: Defeat Tag Master #16.
Shinji (mask form): Defeat him and Hiyori in Tag Master mode.

Movies
Complete the indicated task to unlock the corresponding movie.

Movie 1: Obtain 10,000 Tag points with at least one Human character in the team.
Movie 10: Obtain 25,000 Tag points a second time with a different team of one Shinigami character and one Human character.
Movie 2: Obtain 10,000 Tag points a second time with at least one Human character in a different team.
Movie 3: Obtain 10,000 Tag points with at least one Hhinigami character in the team.
Movie 4: Obtain 10,000 Tag points a second time with at least one Shinigami character in a different team.
Movie 5: Obtain 10,000 Tag points with at least one Arrancar character in the team.
Movie 6: Obtain 10,000 Tag points a second time with at least one Arrancar character in a different team.
Movie 7: Obtain 10,000 Tag points with at least one Vizard character in the team.
Movie 8: Obtain 10,000 Tag points a second time with at least one Vizard character in a different team.
Movie 9: Obtain 25,000 Tag points with a team of one Shinigami character and one Human character. 

Stages
Complete the indicated task to unlock the corresponding stage.

Hueco Mundo Desert: 5,000 points
Las Noches - Aaroniero's Room: 22,000 points
Las Noches - Cirucci's Room: 12,000 points
Las Noches - Dordonii's Room: 17,000 points
Las Noches - Outside: 25,000 points
Las Noches - Room of Doors: 8,000 points
Las Noches - Sousuke Aizen's Room: 40,000 points