This song was inspired by the Nick Tosches novel of the same name. Published in 2012, Me and the Devil is the fifth novel written by the American journalist, novelist and biographer. His 1982 biography of Jerry Lee Lewis, Hellfire, was named "the best rock n' roll biography ever written" by Rolling Stone.
Frontman Jon Fratelli told Billboard magazine this track had four different incarnations before the final version that was recorded for the album. "I'm quite happy we waited until it was right," he said. "Some things, you need not push them; you need to let them arrive somewhere, and that one definitely kind of arrived."
Phil Oakey recorded his vocals for "Don't You Want Me" in the studio bathroom. The recording was disrupted by guitarist Jo Callis reaching through an open window from outside to repeatedly flush one of the toilets.