(* means:) Playable in Musou Mode, Free Mode and Challenge Mode. Others playable in only Free Mode and Challenge Mode.

Character	How to unlock
Cao Cao(*)	Clear Musou Mode with three Wei characters.
Cao Pi	Defeat Cao Pi within 5 minutes on Sun Jian side of He Fei.
Cao Ren	Succeed in Battle Objective 2 on the Lu Bu side of Fan Castle.
Diao Chan(*)	Clear Musou Mode with 1 character from each Kingdom.
Dong Zhuo	Succeed in Battle Objective 1 on the Lu Bu side of The Battle of Hu Lao Gate.
Gan Ning(*)	Clear Musou Mode with 1 Wu character.
Guan Ping	Succeed in 2 battle objectives on the Shu side of Fan Castle and finish battle with Guan Ping alive.
Huang Gai	Succeed in Battle Objective 3 on the Wu side of The Battle of Chi Bi.
Huang Zhong	Succeed in 1 battle objective on the Wei side of Ding Jun Mountain.
Ling Tong	Succeed in Battle Objective 1 on the Wei side of the Battle of Shi Ting.
Liu Bei(*)	Clear Musou Mode with 3 Shu characters.
Lu Bu(*)	Clear Musou Mode with Liu Bei, Cao Cao, Diao Chan, and Sun Jian.
Lu Meng	Succeed in 2 battle objectives on the Wei side of He Fei.
Ma Chao	Succeed in 2 battle objectives on the Wei side of Han Zhong Attack Defense Battle.
Pang Tong	Succeed in 3 battle objectives at Cheng Du battle and finish battle with Pang Tong alive.
Sun Ce	Succeed in Battle Objective 1 on the Sun Jian side of the Battle of Xia Pi.
Sun Jian(*)	Clear Musou Mode with 3 Wu characters.
Sun Quan	Succeed in Battle Objective 1 on the Lu Bu side of The Battle of Chi Bi.
Taishi Ci	Defeat him in the Battle for Wu Territory.
Wei Yan	Succeed in 2 battle objectives on the Shu side of WuZhang Plains and finish battle with Wei Yan alive.
Xiahou Yuan	Succeed in 1 battle objective on the Shu side of Ding Jun Mountain.
Xiao Quio	Succeed in Battle Objective 3 on the Wu side of the Battle of Shi Ting.
Xu Chu	He Fei, Wu side, Personally kill Cao Ren and Xu Chu.
Xu Huang	Succeed in 2 battle objectives on the Wei/Wu side of Fan Castle.
Yuan Shao	As Wei, complete all 3 targets and capture Wu Chao before completing the stage.
Yue Ying	Succeed in Battle Objective 1 on the Wei side of the Battle of Wu Zhang Plains.
Zhang Jiao	Beat stage with completing all three targets in the Yellow Turban Rebellion.
Zhang Liao(*)	Clear Musou Mode with 1 Wei character.
Zhen Ji	Succeed in Battle Objective 1 on the Lu Bu side of the Xu Du Invasion.
Zheng He	Succeed in 2 battle objectives on the Shu side of Han Zhong Attack Defense Battle.
Zhou Tai	Succeed in 3 battle objectives on the Shu side of Yi Ling.
Zhuge Liang(*)	Clear Musou Mode with 1 Shu character.