Kepner Funeral Homes said Williams died Monday at his home in Wheeling. Funeral arrangements were incomplete.
According to his website, Williams was born in Cleveland, Ohio, in 1914 as Andrew John Smik. He came to Wheeling in 1937 to audition for radio station WWVA-AM. He and his late wife, Chickie, became one of the most popular acts for WWVA and its show that later became known as Jamboree USA.
Williams quit school in the 10th grade to help support his family. He worked alongside his father in the coal mines but left to pursue an entertainment career.
In a 2008 interview with The Intelligencer newspaper, Williams said his grandmother bought him his first professional guitar in 1933 and he started performing at square dances in small Pennsylvania towns.
"When President Roosevelt lifted the prohibition laws, I was able to play guitar at beer gardens for $1 a night," he said.
After performing on radio stations and at beer gardens with various acts, Williams formed the Border Riders and started broadcasting a 2:45 p.m. daily show on WWVA in 1937. He and his wife married two years later and they became the Jamboree's headline act that could be heard on AM radio from Canada to Florida.
Williams began touring in 1949, taking his act to northern Maine and Canada.
"When Wheeling businessmen would go to Canada, they would always get discounts because the people knew our show," Williams said.
Williams' daughter, Barbara Smik, told The Intelligencer that he had opportunities to go elsewhere but he considered Wheeling and West Virginia as his home.
Chickie Williams died in November 2007 at age 88. In 2008 the state renamed a section of road in Wheeling as the "Doc and Chickie Williams Highway; Country Music Royal Couple."
The couple was inducted into the West Virginia Music Hall of Fame in 2009.