What do you call a set of Surrealists?

It sounds like a trick question, but it's not. If you make your way to the Scottish National Portrait Gallery in Edinburgh, you will find The Surrealist Chessboard, a photographic work created in 1934 by 20th-century avant-garde photographer Man Ray.

Stacked five-deep and four-square are black-and-white head shots of the artists and writers at the forefront of the Surrealist movement. They include a sharp Salvador Dali, an endearingly punkish Yves Tanguy, a serious Picasso – with distracting comb-over – and, in the bottom right-hand corner, Man Ray himself, looking down on his ubiquitous camera. All their heads have been glued on by Man Ray and he has scribbled all their names at the bottom, along with annotations. There is even an inky thumbprint at the top of the page.

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The exhibition, Man Ray Portraits, also features images of some of the greatest names in 20th-century art, literature, music, cinema and fashion. Featuring striking images of Marcel Duchamp, André Breton, Max Ernst, Jean Cocteau, James Joyce, Erik Satie, Henri Matisse, Igor Stravinsky, Aldous Huxley and more, this is a snapshot of a heady world peopled by individuals who lived life to the full.

There are Man Ray's women too. He had many lovers and muses, including fashion model turned photographer, Lee Miller, with whom he collaborated on some of his finest work. The show also includes portraits of Virginia Woolf, Gertrude Stein and Coco Chanel.

Another lover, Kiki de Montparnasse, is immortalised in an image known as Noire Et Blanche, in which her pale, sleeping face rests on a tabletop beside a carved ebony African mask. Man Ray's last muse, his wife Juliet, whom he met in 1940, also appears in images which capture the glamour of the artist's years in Hollywood between 1940 and 1950.

There are more than 100 works on show, drawn from major international museums and private collections across the world. The exhibition charts Man Ray's long career from early photographs, taken in New York in 1916, to his last portraits shot in Paris in the 1960s.

Although he viewed himself primarily as a painter, Man Ray made his living as a photographer for leading fashion and cultural periodicals of the day. There are original copies on show of Vanity Fair, Harper's Bazaar and Vogue, and more specialised art journals such as Minotaure and Littérature, to which he regularly contributed.

Portrait Gallery curator Terence Pepper sourced many of these from eBay and they provide the detail which makes this exhibition shine like a new photographic plate. One copy of Harper's Bazaar, from 1934, features a series of Man Ray photographs – the first to be "wired" by shortwave radio from Europe to the US – and gives a snapshot of his view of that year's Paris collections.

Born Emmanuel Radnitzky in Philadelphia in 1890, Man Ray was the son of Russian-Jewish immigrants who both worked in the rag trade: his father as a tailor and his mother as a seamstress. When the family moved to Brooklyn, his father changed the family name to Ray. By the time he was working as a commercial artist in New York, young 'Manny' had became Man.

After meeting the French artist Marcel Duchamp in New York in 1915, his growing interest in Surrealism was given full reign to develop. This friendship led to the latter's move to Paris in 1921 following the break-up of his first marriage.

There he found his spiritual and artistic home, and quickly became a key figure at the heart of both Dadaism and Surrealism, chronicling its people and its spirit.

He is also credited with inventing, with Lee Miller, the process of solarisation, which partially reverses the light and dark tones in an image and creates a seemingly glowing profile around the subject. The use of this technique can be seen in the portraits on show here of Miller, fashion designer Elsa Schiaparelli, singer and actress Suzy Solidor and his own Self-Portrait With Camera.

This beautiful and thought-provoking exhibition is put to bed with a very Man Ray-ish portrait of French film star Catherine Deneuve from 1968, taken for the Sunday Times Magazine.

Titled The Mysterious Art Of Catherine Deneuve, it surrounds the film star with objects made by the artist. A fitting combination of photographer-in-action meets maker, this picture tells the many stories of Man Ray.

Man Ray Portraits, Scottish National Portrait Gallery, Edinburgh, www.nationalgalleries.org, until September 22