The provocative image was taken by fashion photographer Steven Meisel but was never included in her controversial 1992 book Sex.
The 1990 pic is expected to fetch over £5,000 when it goes under the hammer at Bonhams in New York next month.
Madonna – who would have been around 32 years old when the photo was taken – is featured sporting bleach-blonde hair and dark eye make-up.
A strategically placed bed sheet saves the shot from indecency as she sprawls out starkers on her mattress.