Titled Remember Me Vol. 1, the album is a collection of 14 tracks originally sung by artists like Johnny Cash, George Jones, Webb Pierce and Rosemary Clooney.
Nelson's album also features seven country songs that topped the charts like Cash's 'Sunday Morning Coming Down' and Tennessee Ernie Ford's 'Sixteen Tons'.
Nelson apparently hand-picked the songs, which have been taken from his sessions with producer James Stroud.
The full track list for Remember Me Vol. 1 is:
1. 'Remember Me' (Ernest Tubb)
2. 'Sixteen Tons' (Tennessee Ernie Ford)
3. 'Why Baby Why' (George Jones)
4. 'Today I Started Loving You Again' (Merle Haggard)
5. 'I'm Movin' On' (Hank Snow)
6. 'That Just About Does It' (Vern Gosdin)
7. 'This Old House' (Rosemary Clooney)
8. 'Sunday Morning Coming Down' (Johnny Cash)
9. 'Smoke That Cigarette' (Tex Williams)
10. 'Slowly' (Webb Pierce)
11. 'A Satisfied Mind' (Porter Wagoner)
12. 'Roly Poly' (Bob Wills & His Texas Playboys)
13. 'Release Me' (Ray Price)
14. 'Ramblin' Fever' (Merle Haggard)
15. 'More and More' (Webb Pierce) *iTunes exclusive
Monster's Ball actor Billy Bob Thorton filmed a documentary about Nelson called The King of Luck, in which he calls the country singer "a legend".
Last year, Nelson was arrested for possession of marijuana and could face a two-year sentence. His proposed plea deal was rejected by a Texas judge in July.
Remember Me Vol. 1 will hit stores on November 21 with a follow-up album reportedly expected to be released in 2012.
Watch the video for Willie Nelson's 'I'm A Worried Man' featuring Toots Hibbert below: