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Walker was born in Ralls, Texas on January 14, 1929 and was the youngest of three children. His mother died when he was only six years old, and Billy's father was unable to care for him and his two older brothers. Some of the children were placed in a Methodist orphanage in Waco, Texas. Billy attended High School in Whiteface, Texas where he won a talent contest which entitled him to appear on radio in Clovis, NM. Billy was inspired by the music of Gene Autry as a teenager, he began his professional music career in 1947 when he was 18. After his debut on Clovis radio he joined the Big D Jamboree in Dallas in 1949. The same year, Hank Thompson helped him sign with Capitol Records. His manager at the time had him wear a Lone Ranger-style black mask and billed him as The Traveling Texan, the Masked Singer of Country Songs.

In 1951, Walker signed with Columbia Records and the following year joined the Louisiana Hayride in Shreveport, Louisiana, where he and Slim Whitman were responsible in part for Elvis Presley's first appearance on the radio program. In 1954, Walker scored his first hit with "Thank You for Calling". His early Columbia recordings were at a Dallas studio owned by producer Jim Beck, responsible for hits by Ray Price, Lefty Frizzell and others.[3] In 1955, Walker, Presley and Tillman Franks teamed up for a tour of West Texas. Walker soon became a cast member of ABC-TV's Ozark Jubilee in Springfield, Missouri, where he began a long friendship with host Red Foley.

In the late 1960s, he hosted a syndicated television show, "Billy Walker’s Country Carnival", and appeared on other country music TV programs. Walker performed around the world, and several times during the 1980s sang at the International Festival of Country Music at Wembley Arena in London. In April 2006, Walker recorded the duet "All I Ever Need Is You" with Danish singer Susanne Lana for Hillside House Records. The recording, at Signal Path Studio in Nashville, Tennessee, was produced by Charlie McCoy.

Walker continued to tour and remained a mainstay on the Grand Ole Opry. On May 21, 2006, Walker died in a car accident when the van he was driving back veered off Interstate 65 in Fort Deposit Alabama and overturned. He was scheduled to perform with Terri Clark, Porter Wagoner and others two days after his death. His wife Bettie; bassist Charles Lilly Jr., son of Everett Lilly of The Lilly Brothers; and guitarist Daniel Patton were also killed He was scheduled to perform with Terri Clark, Porter Wagoner and others two days after his death.