Born Andrew John Smik in Cleveland, Williams had a long career with the Wheeling Jamboree radio show. He grew up in Pennsylvania and began performing on radio in Pittsburgh before moving to WWVA in Wheeling in 1937 with his band, the Border Riders.

The group included his wife, Chickie Williams, his brother Cy, and others. They toured widely, especially in the Northeast and Canada. Doc was known for emotional songs like "My Old Brown Coat" and "Willie Roy, the Crippled Boy," while Chickie had a big hit with "Beyond the Sunset" in 1947.

To help keep traditional country music alive, he started Wheeling Records and opened Doc Williams Country Store in the 1970s. He and Chickie were inducted into the West Virginia Music Hall of Fame in 2009.