Launching in February, the landmark commemoration will include well-known models as well as celebrating the photographers who captured them.
Paying tribute to controversial famous shots, 'Vogue 100: A Century of Style' will be an exhibition of 280 prints from the Condé Nast archives.
Aside from famous faces, it will also honour fashion and photography, aiming to tell the story of how the magazine has changed over a century.
Kate Moss will be featured more than once in the exhibition. A more recent photo taken by Mario Testino in 2008 (above) will show the shot of her stood against a wall holding up her skirt.
Dr Nicholas Cullinan, Director of the National Portrait Gallery, London, said: "British Vogue has played a pivotal role in the development of photographic portraiture over the past century, commissioning leading photographers and designers to produce some of the most memorable and influential images in the history of fashion."
Claudia Schiffer will be present in the gallery, featured on a motorbike wearing a lacy slip in 1989 while more recent shots will show how Lara Stone has excelled in the latest generation of models.
Other famous faces will include Gwyneth Paltrow and David Beckham to show the magazine doesn't just focus on models on the catwalk.
Ranging from the bizarre to the stunning, we're pretty excited to have a snoop on the photos that made the cut.
Vogue editor-in-chief Alexandra Shulman said: "I am incredibly proud of this collection of exceptional photography and of the whole concept of the exhibition, which shows the breadth and depth of the work commissioned by the magazine as well as Vogue's involvement in the creation of that work.
"Anybody interested in photography, fashion, fame and magazines will find this an unmissable experience."
Leading photographers, including Cecil Beaton, Lee Miller, Irving Penn and Snowdon, will be on display.
Sponsored by Leon Max, the exhibition will open on 11 February and run until 22 May.