The fifth Desert Sessions EP was recorded in sessions between March 11 and 14, 1999 at Rancho De La Luna in Joshua Tree, California, a studio founded by Fred Drake and Dave Catching. The tracks on Volume 5 were engineered by Steve Feldman, with Tony Mason assisting, and features a total of eleven credited musicians: Josh Homme (bass, guitar and keyboards), Catching (guitars and piano), Blag Jesus, Mario Lalli, Nick Oliveri (all vocals), Gene Trautmann, Brant Bjork, Drake, Adam Maples, Mathias Schneeberger (all drums) and Mason (guitar and bass). Homme mixed the album, and it was mastered by Dave Schultz at DigiPrep in Hollywood, Los Angeles, California.
Volume 5 was initially released alone on vinyl by Man's Ruin Records on July 21, 1999. It later received a re-release with its follow-up, Volume 6: Black Anvil Ego, on CD on September 14, 1999 as Volumes 5 & 6.