The images by photographers such as Helmut Newton, Mario Testino and Rankin are to be auctioned to raise funds for the charity 'Crisis' supported by Prince William.
The young royal will also see one of his own photographs sold in the auction. Together with a previously homeless man, Jeff Hubbard, the Prince created the 'Crisis Royal Diptych' which features an image of each of them taken by the other.
The other shots, both vintage and contemporary include one of Hepburn riding a camel in a gown with a thigh split and one of Moss wearing a torn veil.
The close-up of the British beauty taken in 1993 in Marrakech by Albert Watson is one of the star attractions of the collection.
The Prince himself will be attending a reception to launch the sale on Thursday for the charity, of which he is a patron.
Other artists and photographers whose work will be sold at the auction at Christie's in London include Henri Cartier Bresson, Terence Donovan, Wim Wenders and Patrick Demarchelier.
All proceeds of the exhibition will go to Crisis, the UK's leading homeless charity for single people.
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