He studied law under Briscoe Baldwin in Staunton, Virginia, and was admitted to the bar.[1] During the Civil War, he was elected by the legislature of Virginia to be a member of the Confederate States Senate in which he sat until 1865.[1] After the war, he was the first ex-Confederate elected to the United States Senate, entering office as a Democrat from West Virginia, from March 4, 1875, until his death.[5][7] Caperton died of heart disease at his room on I Street NW in Washington, D.C., on July 26, 1876.[1][3] His residence near Union, "Elmwood," was listed on the National Register of Historic Places in 1976.