Born in Ashland, Kentucky, Whitley grew up in nearby Sandy Hook, Kentucky. Whitley began his career there in 1970, performing in Ralph Stanley's band. Establishing himself as a lead singer in bluegrass music, Whitley moved to Nashville, Tennessee, in 1983 and began his recording career there. His first Top 20 Country Hit single, "Miami, My Amy", was released in 1986. While touring for his album L.A. to Miami, he married country singer Lorrie Morgan. In 1988, his first three singles from his studio album Don't Close Your Eyes, the title song, "When You Say Nothing at All" and "I'm No Stranger to the Rain" were number-one hits. On May 9, 1989, he suffered alcohol poisoning at his home in Nashville, and died as a result. His death came in the wake of several years of alcoholism. His later two singles, "I Wonder Do You Think of Me" and "It Ain't Nothin'", were released after his death.
Whitley was born to Faye (editor of The Elliott County News) and Elmer Whitley (an electrician) in Ashland, Kentucky, but was raised 46 miles away in Sandy Hook, and attended Sandy Hook High School. He had two brothers, Randy and Dwight, and a sister, Mary. The Whitley family has lived in the Elliot County area since the 1840s.
As a teenager in Sandy Hook, Whitley and his friends would pass the time drinking bootleg bourbon and racing their cars down mountain roads at dangerous speeds. Whitley was once in a car whose driver attempted to round a curve at 120 mph. The car wrecked, killing his friend and almost breaking Whitley's neck. In another incident, he drove his car off a 120-foot cliff into a frozen river, escaping with only a broken collar bone.
In 1969 he performed in a musical contest in Ezel, Kentucky, with brother Dwight on five-string banjo. Ricky Skaggs was also in the contest. Skaggs and Whitley hit it off right away and quickly befriended each other.
Fifteen-year-old Whitley and 16-year-old Skaggs were discovered in Ft. Gay, West Virginia by Ralph Stanley who was 45 minutes late for a show due to a flat tire. Stanley opened the door of the club and heard what he thought were the Stanley Brothers playing on a jukebox. However it was Whitley and Skaggs, who "sounded just like me and Carter in the early days". The two soon joined Ralph's band. Whitley became lead singer for Stanley in 1974. Whitley also played with J.D. Crowe & the New South in the mid-1970s. During this period, he established himself as one of the most versatile and talented lead singers in bluegrass. His singing was heavily influenced by Carter Stanley and Lefty Frizzell. He moved to Nashville in 1983 to pursue a country music career and soon signed a record deal with RCA Records.