Born in Pulaski County, Kentucky, Williams moved with his parents to Wayne County. He received a limited education. Learned the trade of brickmaker in Monticello when about fifteen years of age. He studied law. He was admitted to the bar and practiced. He served as member of the State house of representatives 1829-1834 and in 1846.
Williams was elected as an Anti-Jacksonian Whig to the Twenty-fourth, Twenty-fifth, and Twenty-sixth Congresses (March 4, 1835 - March 3, 1841). He served as chairman of the Committee on Invalid Pensions (Twenty-sixth Congress). He was not a candidate for reelection. Williams died on November 1, 1876, in San Jose, California and is buried in the Colma Cemetery, San Mateo County, California.