Acclaimed Scots artist Peter Howson has produced several portraits of the pop icon in a state of undress.
Madonna & Guy was painted in 2005. The couple parted last year.
In it the singer is reclining and film director Ritchie has a hand on her thigh.
McTear's auction house in Glasgow said it expected the work to fetch up to £22,000 when it goes on sale on Saturday.
It is being sold by a private collector.
Brian Clements from the auctioneers said: "There is no doubt that the recent split of Madonna and Guy has generated increased interest in the painting.
"The painting created a huge amount of controversy when it was unveiled a few years ago and I think it's safe to say it is one of a kind."
What began in 2000 as a fairytale wedding at Skibo Castle in the Scottish Highlands came to an end in November when the couple were granted a "quickie" divorce.
They share custody of their two boys, Rocco and adopted son David Banda.
The McTear's Scottish Contemporary Art Auction features a host of other works by former official war artist Howson.
The painter's past customers are said to include David Bowie and Mick Jagger.
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