The nude image of the Queen of Pop was taken in 1990 by Steven Meisel, who worked on the 58-year-old pop star's Sex book in 1992. It was previously purchased by its current owner from a New York gallery.
Measuring 21.5 inches by 19 inches, the photograph shows the singer reclining on a bed with her breasts exposed and just a white sheet covering her bottom half, the Daily Mail reported.
The picture is to be sold by Bonhams, who described it as "absolutely stunning".
"It is just a beautiful tone of grey. It is not just black and white it is grey and silvery. Madonna was posing for a number of photographers at the time this was taken in the 1990s when she was in her early 30s. She was going through a phase of having bleach blonde hair and heavy dark eye make-up that gave her a dramatic look - and of course she has a gorgeous body.
"She is a very healthy person and I'd imagine the cigarette is just a prop to make her look sexy and sultry. There are Madonna superfans and devotees across the world who would love to own it," said Judith Eurich from Bonhams. PTI CORR BK