The 12 paintings in the sale have never appeared at auction before.
They will go under the hammer at the Bonhams saleroom in Edinburgh on March 31 for an estimated £800,000 to £1.2 million.
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The paintings, which are being sold by an anonymous collector, offer a cross-section of the themes that have informed the self-taught artist’s work for many years.
Chris Brickley, Bonhams’ head of Scottish art, said: “This is one of the most comprehensive collections of Vettriano’s work ever assembled, covering all the major periods of the artist’s career and giving a vivid insight into his artistic development.
“This is the most important collection of Jack Vettriano’s work to appear at auction for the past 10 years.
“It spans the period when the artist was producing some of his most recognisable and best-loved images.
“Several of the paintings, for example Waltzers and Missing Man II, will be familiar from books about Vettriano and the very popular cards and posters which have been made from his work.”
Waltzers (estimated at £200-300,000) shows elegant couples dancing under a night sky while The Road to Nowhere (estimated at £150-200,000) and Missing Man II, which could fetch up to £150,000, show stylish figures on beaches.
Not all the works are dated but the earliest one that is dated is 1992 and the latest 2004.
Vettriano, born in 1951, left school at 16 and did not take up painting full-time until the age of 40.
The artist, who grew up in Methil, Fife, first found fame in 1989 when two of his canvases submitted to the Scottish Royal Academy sold on the first day.
His work has since featured in exhibitions in Edinburgh, London and New York. He was made an OBE in 2003.
One of his most famous paintings, The Singing Butler, sold for £744,000 in 2004 and is one of the best-selling posters in Britain.
More than 123,000 people flocked to see a retrospective of his work at Kelvingrove Art Gallery and Museum in Glasgow between September 2013 and February 2014, making it the most visited art exhibition at the institution.
Actor Jack Nicholson and football legend Sir Alex Ferguson are among the owners of Vettriano’s work.
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