If you complete the task listed next to each character in Scenario Campaign mode, then you will unlock that character in the Arena stage.
Anna: Defeat her in G Corporation, Millennium Tower.
Armour King: Defeat him in Lost Cemetery.
Asuka: Defeat her in Kazama-Style Traditional Martial Arts Dojo.
Baek: Defeat him in West Coast Canal Industrial Complex.
Bob: Defeat him in Central District, 11th Avenue.
Bruce: Defeat him in G Secutiry Service, Operations Headquarters.
Bryan: Defeat him in Southern Woodlands.
Christie: Defeat her in Seahorse Grand Hotel.
Devil Jin: Defeat him in Nightmare Train.
Dragunov: Defeat him in container Terminal 7.
Eddy: Defeat him in Tekken Force 4th Special Forces Operation Group Compound.
Feng: Defeat him in Deserted Temple.
Ganryu: Defeat him in Aranami Stable.
Hwoarang: Defeat him in Industrial Highway 357.
in Heihachi Arena: Defeat him in Mshima Estate.
Jack-6: Defeat him in Container Terminal 3.
Jin: Defeat him in Azazel's Temple, Central Corridor.
Julia: Defeat all enemies in G Science and Technology, Research Building 3.
Kazuya: Defeat him in G Corporation, Millennium Tower Heliport.
King: Defeat him with Marduk in Mixed Martial Arts Gym "Wild Kingdom".
Kuma or Panda: Defeat Kuma in North Nature Park.
Law: Defeat him in West District, Chinatown.
Lee: Defeat him in Violet Systems.
Lei: Defeat all enemies in ICPO Branch Office.
Leo: Defeat it in 16th Archaeological Expedition's Excavation Site.
Lili: Defeat her in Queen's Harbour.
Marduk: Defeat him with King in Mixed Martial Arts Gym "Wild Kingdom".
Miguel: Defeat him in South Bay Warehouse Area.
Mokujin: Defeat it in Subterranean Pavillion.
Nina: Defeat her in Mishima Zaibatsu, Central Subway Line.
Paul: Defeat him in West District, 13th Avenue.
Raven: Defeat him in Secret Underground Passage.
Roger Jr.: Defeat it in Mishima Industries, Biotech Research Station Ruins.
Steve: Defeat him in Abyss Gate.
Wang: Defeat him in Fujian Tulou.
Xiaoyu: Defeat her in Mishima Polytechnic.
Yoshimitsu: Defeat him in Kigan Island.
Zafina: Defeat all enemies in Mystic's Village.
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