Williams worked on farms and as a school teacher from 1876 to 1887, spending some time (1879–80) taking classes at West Virginia University.
In 1888 he moved back to Greenbrier County, West Virginia and opened a practice in Lewisburg.
He married three times: to Minnie J. Patterson (died 1892) in 1883; to Mary (Dice) Leonard (d. 1906) in 1894; and then to Harriet Peck.
Williams and his first wife had two sons, Russell and Forest, and a daughter, Florence.
[4] Forest, born 1892, was a member of the 6th Marine Regiment and died of wounds received on July 19, 1918, during a bloody attack on German lines.