• Sir Sean Connery acted as a life model for strudents
It was painted in 1951 when the James Bond star, now 80, was working as an unknown nude model for Edinburgh students.
The oil on canvas - thought to be worth thousands of pounds - was among more than 500 works discovered by relatives of artist Rab Webster who died last month aged 83.
He was a student at Edinburgh College of Art when Connery posed there shortly before his big break in the stage production of South Pacific which eventually led to the role of Bond and international stardom. The collection of Mr Webster - a former art teacher at Selkirk High School in the Borders - is set to go on public display for the first time.
Nick Bihel, who is married to Mr Webster's niece Heather, said: "There were a few sketches of Sean Connery which are distributed among the family so to speak.
"The oil painting was part of a whole load of paintings just stacked on top of each other in a studio he used as a dark room. He never sold or exhibited any of his paintings but it is fairly obvious he was a very talented artist.
"I remember Rab telling me about Sean Connery posing for the students. He said Connery treated it just as a job and that he didn't say very much. I have no idea how much the painting of Sean Connery would be worth. At the moment we are just taking stock of the situation but we would like to put them on display in Selkirk. Obviously, some will have to be sold as there are just too many to keep them all."
Mr Bihel said Mr Webster, who was principal of art at Selkirk High, stopped producing paintings after 1968. He stayed with Mr Bihel and his wife at their home in Selkirk for the last eight months of his life.
Mr Bihel said: "He just had so many other interests.
"But I know he never sold a single painting or held any exhibitions of his own work. He would donate the odd painting now and again to a charity but that was all.
"The paintings cover a range of topics including landscapes done of places like Harris, Tiree and Pittenweem to portraits, like the one of Sean Connery."
The 20in by 28in work shows a back view of Connery, who is wearing a thong. His face, which looks to the left, is partially obscured. Mr Bihel said: "I recognised him instantly. The painting already shows his receding hairline."
He said he was "not surprised" to find it. "I had already seen the sketches a few years ago. I think it looks good."
Mr Webster was also renowned as a rugby coach, an authority on the works of Robert Burns, and was learning Gaelic, French and Welsh before he died.
Edinburgh-born Connery had several jobs, including that of artist's model, before he became a film star.His first job was as a milkman in Edinburgh with St Cuthbert's Co-operative Society. He also served in the Royal Navy and worked as a lorry driver, a labourer and a coffin polisher.
Connery also took up bodybuilding as a hobby and took part in a Mr Universe contest in the 1950s. It was then that one of the other competitors mentioned that auditions were being held for a production of South Pacific.