Mary Frances Williams was born in Atlanta, Georgia. She graduated from Marietta High School. She earned a bachelor's degree from Earlham College in 1976 and a master's degree from the University of Georgia in 1981. Her career experience includes working as a public policy consultant and a director of advocacy. She has served as a board member of Women's Policy Group. As of 2024, Williams was affiliated with Leadership Cobb and Leadership Georgia.
