Mary Alicia Rhett was born on February 1, 1915, in Savannah, Georgia, to Isobel Murdoch, an immigrant from Liverpool, England, and Edmund M. Rhett, an American army officer and engineer. After her father's death during World War I, Alicia and her mother moved to Charleston, South Carolina.

Alicia Rhett became a theatre actress in Charleston and graduated from Memminger High School. During a performance of "The Recruiting Officer" in 1936, she was spotted by Hollywood director George Cukor, who was impressed by her charm and beauty.

Alicia Rhett auditioned for the part of Melanie Hamilton in "Gone with the Wind," but the role went to Olivia de Havilland. In March 1937, Cukor offered Rhett the role of India Wilkes, sister of Ashley Wilkes. After the success of "Gone with the Wind," Rhett left Hollywood and returned to South Carolina, retiring from filmmaking in 1941, citing a lack of suitable roles. 

She later became an accent coach for aspiring actors and a radio announcer at station WTMA in Charleston. Prior to appearing in "Gone with the Wind," Rhett showed talent as a sketch artist and portrait painter. Between takes on "Gone with the Wind," she made sketches and drawings of her fellow actors. Soon, Rhett was creating portraits of American servicemen in the Charleston vicinity.

Alicia Rhett died at age 98 of natural causes on January 3, 2014, at Bishop Gadsden Episcopal Retirement Community in her longtime hometown of Charleston, South Carolina. In her obituaries, she was cited as having been "the oldest living actor from Gone With the Wind," being 17 months older than Dame Olivia de Havilland.