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Born in Texas, Duvall began acting after being discovered by director Robert Altman, who was impressed with her upbeat presence and cast her in the black comedy film Brewster McCloud (1970). Despite her hesitance towards becoming an actress, she continued to work with Altman, appearing in McCabe & Mrs. Miller (1971) and Thieves Like Us (1974). Her breakthrough came with Altman's cult film Nashville (1975), and she earned widespread acclaim with the drama 3 Women (1977), also directed by Altman, for which she won the Cannes Film Festival Award for Best Actress and earned a nomination for the British Academy Film Award for Best Actress in a Leading Role. That same year, she appeared in a supporting role (as a writer for Rolling Stone) in Woody Allen's satirical romantic comedy Annie Hall (1977) and hosted Saturday Night Live.

In the 1980s, Duvall became famous for her leading roles, which include Olive Oyl in Altman's live-action feature version of Popeye (1980) and Wendy Torrance in Stanley Kubrick's horror film The Shining (1980). She appeared in Terry Gilliam's fantasy film Time Bandits (1981), the short comedy horror film Frankenweenie (1984), and the comedy Roxanne (1987). She ventured into producing television programming aimed at children and youth in the latter half of the 1980s, notably creating and hosting the programs Faerie Tale Theatre (1982–1987), Tall Tales & Legends (1985–1987) (which earned her a Primetime Emmy Award nomination in 1988), and Nightmare Classics (1989).

Duvall sporadically worked in acting throughout the 1990s, notably playing supporting roles in Steven Soderbergh's thriller The Underneath (1995) and the Henry James adaptation The Portrait of a Lady (1996), directed by Jane Campion. Her last performance was in Manna from Heaven (2002), after which she retired from acting. Duvall for many years kept out of the public media, keeping her personal life generally private; however, her health issues earned significant media coverage. After a 21-year hiatus from acting, Duvall returned to acting in the horror film The Forest Hills.

She died due to complications from diabetes at her home in Blanco, southwest of Austin, Texas.