Born near Mount Sterling, Kentucky, Williams attended the common schools and graduated from Miami University in Oxford, Ohio, in 1839. He studied law, was admitted to the bar in 1840, and commenced practice in Paris, Kentucky. He served in the Mexican-American War, first as a captain of an independent company attached to the Sixth Regiment of the United States Infantry, and afterward as a colonel of the Fourth Regiment of the Kentucky Volunteers.

Williams was a member of the Kentucky House of Representatives in 1851 and 1853. During the American Civil War he served in the Confederate States Army as a colonel in 1861, and was promoted to a Brigadier General in 1862. He surrendered in 1865 and went on to engage in agricultural pursuits, with residence in Winchester, Kentucky.

Williams again became a member of the State House in 1873 and 1875. He was ran unsuccessfully for Governor of Kentucky in 1875, and was a presidential elector on the Democratic ticket in 1876. He was elected to the United States Senate in 1879 and served from March 4, 1879 to March 3, 1885. He failed in his reelection bid and returned to his agricultural pursuits. He died in Mount Sterling in 1898 and was interred in Winchester Cemetery in Winchester.