When Ann Mathews was born about 1764, in Augusta, Virginia, United States, her father, William Mathews, was 23 and her mother, Frances Crowe, was 19. She married Audley Campbell Maxwell on 30 December 1780, in Tazewell, Virginia, United States. They were the parents of at least 7 sons and 4 daughters. She died in 1829, in Tazewell, Tazewell, Virginia, United States, at the age of 65, and was buried in Tazewell, Tazewell, Virginia, United States.