Sir Sean Connery makes an unlikely poster boy for an important art exhibition opening in London on January 29.

Wearing nothing but a thong and a full head of hair, he appears in a painting dating from 1952 when, as a 22-year-old unknown, he earned his crusts not only by delivering milk - as is generally known - but by posing as a life model at Edinburgh College of Art (ECA).

The painting is a life study by the ECA alumnus and jazz musician Al Fairweather, and one of the highlights in the show, Ten Decades, which celebrates the achievements of the college over the past 100 years.

Some 70 works will be on display by graduates, who include the Scottish colourist Samuel Peploe (with his Green Sea, Iona, 1920); the flower painter Dame Elizabeth Blackadder (three works, including Flowers and Red Table, 1969) and the Pop sculptor Sir Eduardo Paolozzi (a bronze, Newton Measuring the World, c.1990).

More than half the works will be on loan from the Fleming Collection, a selection of modern Scottish art amassed from the late-1960s to the mid-1980s by the Scottish bank Robert Fleming & Co Limited. When the bank was taken over by Chase Manhattan Bank in 2000, a foundation was created to run and, indeed, expand the collection. Since then it has been dubbed “a kind of national gallery of Scotland in exile” on account of the importance of its range of work.

Were it not for Fleming's, and the Fleming-Wyfold Foundation, which still collects contemporary Scottish art, this exhibition would have been virtually impossible to arrange on account of these works having been dispersed, or even, in some cases, destroyed.

Shortly after posing in that cold ECA studio, Sean Connery's career started to warm up when he got himself a role in the chorus line of South Pacific. Ten years later he would achieve global super-stardom as agent 007 in the James Bond films. Recently he was voted the “world's sexiest senior”.

As it happens, Ian Fleming, author of the James Bond books, was a grandson of Robert Fleming, the founder of Flemings Bank, and he, too, has the centenary of his birth this year. In April the Fleming Collection will celebrate it with an exhibition of book covers and film poster art, including many publicity images of Connery looking rather more dashing than he does in Fairweather's austere image.

Ten Decades: Edinburgh College of Art Centenary Exhibition, January 29 to April 5; Bond Bound: Ian Fleming and The Art of Cover Design, April 22 to June 28. Both at the Fleming Collection, 13 Berkeley Street, London W1J 8DU (020-7409 5730), admission free