Note: This game is also titled Shin Sangoku Musou: 2nd Evolution.
# Play as Diao Chen
Successfully complete Si Shui Gate (Dong Zhoug's side) 100% in Free mode to unlock Diao Chen.
# Play as Dong Zhoug
Successfully complete Si Shui Gate 100% in Musou mode to unlock Dong Zhoug.
# Play as Guan Ping
Successfully complete Musou mode with Zhao Yun to unlock Guan Ping.
# Play as Houng Zhong
Successfully complete Musou mode with Zhao Yun to unlock Houng Zhong.
# Play as Jiang Wei
Successfully complete Musou mode with Zhauge Liang to unlock Jiang Wei.
# Play as Liu Bei
Successfully complete the last stage in the fourth column in Musou mode with Shu to unlock Liu Bei.
# Play as Lu Bu
Successfully complete the Battle Of Xia Pi (Dong Zhoug's side) 100% in Free mode to unlock Lu Bu.
# Play as Meng Hou
Successfully complete the Nan Zhong stage 100% in Conquest mode to unlock Meng Hou.
# Play as Pong Tong
Successfully complete the last stage in the fourth column in Musou mode with Shu to unlock Pong Tong.
# Play as Yue Ying
Successfully complete Musou mode with Zhauge Liang to unlock Yue Ying.
# Play as Zhang Jiao
Successfully complete the Yellow Turban stage 100% to unlock Zhang Jiao.
# Play as Zhauge Lang
Successfully complete Musou mode with Zhao Yun to unlock Zhauge Lang.
# Hex Mark horse
Defeat Liu Bei in Si Shui Gate with Dong Zhoug to unlock the Hex Mark horse.
# Red Hare horse
Defeat Guan Yu in Escape Chang Ban Battle with the Yellow Turban force to unlock the Red Hare horse.
# Shadow horse
Defeat Cao Cao in the Battle Of Wan Castle to unlock the Shadow horse.
# Storm horse
Defeat Cao Cao in the Battle Of Xia Pi with the Dong Zhoug force to unlock the Storm horse.