According to AllMusic's Stephen Thomas Erlewine, it is "the first comprehensive, multi-label Waylon Jennings retrospective ever assembled," comprising ninety-two songs recorded between [1958 and 1994, with selections from the majority of the singer's recording career.

The other material on the box set covers Jennings' career chronologically, with songs ranging from his years on RCA's roster to later compositions from his short-lived stay at Epic Records; it ignores, however, the tracks from Jennings albums released on independent labels.

The majority of the singer's charting singles are included in the package, as are collaborations such as "Mamas Don't Let Your Babies Grow Up to Be Cowboys" with Willie Nelson and "Highwayman" with The Highwaymen.

A notable addition is the previously unreleased "The Greatest Cowboy of Them All," a 1978 duet with Johnny Cash which was later recorded by Cash alone for A Believer Sings the Truth (1979) and The Mystery of Life (1991); two others, "It's Sure Been Fun" and "People in Dallas Got Hair," had never been released in the United States.

Nashville Rebel was released on four CDs, with a 140-page booklet and liner notes by Rich Kienzle and Lenny Kaye.