An exhibition about her life and career will open at the central London gallery from July and include family photographs of her at ballet practice and pictures taken during her early days working as a model in London.
Photographs from Life magazine, taken during the making of her 1953 film Sabrina, will also go on show alongside posters for some of her most famous films.
The Belgian-born actress performed at Ciro’s nightclub, which now forms the gallery’s archive and study room, in a series of revues in 1949 and 1950.
The gallery’s deputy director, Pim Baxter, said: “Audrey Hepburn was one of the world’s most celebrated actresses, and I am delighted that the National Portrait Gallery will hold a major photography exhibition exploring the life and work of such a significant and much-loved figure who spent the formative early years of her career in Britain.
“It is particularly appropriate that the exhibition will be staged in such close proximity to where she performed as a young woman at the very start of her career.”
The exhibition runs until October 18.