Born in Caswell County, North Carolina, Williams studied law and was admitted to the North Carolina bar.

He served in the Alabama House of Representatives from 1821 to 1839, was the Secretary of the Board of Trustees of The University of Alabama from 1835 to 1841[2] and was a judge of the Tuscaloosa County court from 1832 to 1842.

He was a brother of Mississippi Territorial Governor Robert Williams (1766–1836).

On October 26, 1798, in Caswell County, North Carolina, he married Agnes Payne (1775–1850), a first cousin of Dolley Madison, and they raised 9 children.

He died in Tuscaloosa in 1850 and is buried in Greenwood Cemetery.