- Sam Worthington as Corporal Jake Sully. Sully is a disabled former Marine who becomes part of the Avatar Program. His military background helps the Na'vi warriors relate to him.
- Stephen Lang as Colonel Miles Quaritch. Quaritch is the head of the mining operation's security detail. Fiercely loyal to his military code, he has a profound disregard for Pandora's inhabitants that is evident in both his actions and his language.
- Sigourney Weaver as Dr. Grace Augustine. Augustine is an exobiologist and head of the Avatar Program.
- Michelle Rodriguez as Trudy Chacón. Chacón is a combat pilot assigned to support the Avatar Program who is sympathetic to the Na'vi.
- Giovanni Ribisi as Parker Selfridge. Selfridge is the corporate administrator for the RDA mining operation.
- Joel David Moore as Dr. Norm Spellman. Spellman is a xenoanthropologist who studies plant and animal life as part of the Avatar Program.
- Dileep Rao as Dr. Max Patel, a scientist who works in the Avatar Program and comes to support Jake's rebellion against the RDA.
Na'vi
- Zoe Saldana as Neytiri. Neytiri is the daughter of the Omaticaya leader, the Na'vi clan central to the story, who is attracted to Jake because of his bravery while being frustrated.
- C. C. H. Pounder as Mo'at. Mo'at is the Omaticaya's spiritual leader, Neytiri's mother, and consort to clan leader Eytukan.
- Wes Studi as Eytukan. Eytukan is the Omaticaya's clan leader, Neytiri's father, and Mo'at's mate.
- Laz Alonso as Tsu'tey. Tsu'tey is heir to the chieftainship of the tribe, and at the beginning of the film's story he is betrothed to Neytiri.
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