The image features a waif-like Kate Moss posing suggestively against some fairy lights and it sparked a "heroin chic" movement of which the iconic model became a leading light.
The now infamous Vogue fashion shoot of 1993, which was denounced by some as a celebration of a model who appeared "paedophilic and almost like a junkie", will be part of a new exhibition at the National Portrait Gallery, telling the story of contemporary fashion photography through seminal portraits of the world's top models and Hollywood celebrities, taken by the fashion photographers Corinne Day, Mario Sorrenti, Steven Klein, Paolo Roversi and Mert Alas & Marcus Piggott.
The show, Face of Fashion, running from 15 February until 23 May next year, aims to examine and subvert the idea of glamour, beginning with a portrait of a young Moss in one of her first shows for Face magazine in 1990. Other photographs will include an image of Lauren Hutton taken by Sorrenti with her leg in a contortion, a gothic pose of Nina Ricci by Mert & Marcus, with lipstick smeared on her cheek, a close-up of an ageing Catherine Deneuve and a picture of the pop star Justin Timberlake, with shaved hair and a nose bleed.
The architect David Adjaye, one of this year's Stirling Prize nominees, will be designing a "surprise installation" for the show.
Many of the 120 portraits include those originally produced for fashion houses, while some were commissioned for magazines such as Vanity Fair and Pop.
But others reveal intriguing insights into the inner life of the glamorous sitters. An intimate portrait by Klein of Angelina Jolie features the actress stretched languorously on a bed with Brad Pitt standing nearby, while another captures the unguarded facial expression of a model who is leaning against a wall during a break in a fashion shoot.
Susan Bright, the curator of the exhibition, said the work followed a tradition of portraiture in magazines by the likes of David Bailey and Helmut Newton.
"This is a look at the way we see things by taking these images out of the context of magazines and putting them in a gallery," she said. "Some describe the cross-over of glamour and anti-glamour. The five photographers work very differently... three of the five have taken pictures of Kate Moss and it is interesting to look at the different way she is presented. Corinne Day, for example, has a very beautiful, intimate approach to portraiture; she almost falls in love with her sitters, and you see these moments of friendship in the main body of her work."
Sandy Nairne, the director of the NPG, said following the success of the solo exhibition showing the works of the fashion photographer,Mario Testino a few years ago, this exhibition was the first of its kind to fully examine the "innovation and diversity" of current fashion portraiture.
"We have extracted the works of five fantastic photographers. Fashion surrounds us... its place in our society is undeniable. There have been many other exhibitions about the fashion field but this is the first time the focus is on portraiture," he said.
Mr Nairne also referred to changes within the stipulations for next year's BP Portrait Award, previously only open to younger artists, but now extended to those of any age.