Jewellery, paintings, couture clothing, books and furniture are among the items which have been passed down through the double Oscar-winner’s family.
In a statement, they said: “We hope people take as much pleasure from this collection as our grandparents, parents and families have done.”
Items going under-the-hammer, at Sotheby’s in London, include Leigh’s personal copy of the Gone With The Wind novel, given to her by its author Margaret Mitchell and expected to fetch up to £7,000.
Having always been a fan of the book, the English actress kept a copy close at hand while filming the movie and resented any divergence from the text.
She once said she had been “fascinated by the lovely wayward, tempestuous” Scarlett O’Hara, the character she would go on to play, “from the moment” she read the novel.
“I felt that I loved and understood her.... When I heard that the book was to filmed....I longed to play the part,” she said.
Mitchell inscribed a poem in the book to the English actress, writing: “Life’s pattern pricked with a scarlet thread / where once we were with a grey / To remind us all how we played our parts / In the shock of an epic day”.
Leigh went on to win the first of her two Oscars for her 1939 performance, aged 26, as the feisty O’Hara.
Also up for sale is Leigh’s gold ring, estimated to fetch £600, marking her famously passionate relationship with actor Laurence Olivier.
It is inscribed with the words “Laurence Olivier Vivien Eternally”.
The pair met in 1935, while married to other people, and embarked on an affair.
They wed in 1940 and stayed married for 20 years.
Olivier described the actress as having “an attraction of the most perturbing nature I had ever encountered” while Leigh had predicted before even meeting the actor: “That’s the man I’m going to marry”.
Another lot is a red chalk drawing of Leigh, famed for her beauty, for a painting commissioned by Olivier.
But the painting was never finished because Olivier allegedly thought the artist, Augustus John, had become too infatuated with his subject.
Other items up for auction include a silver cigarette box given to Leigh, then a relatively unknown actress, by the man credited with securing her the role of heroine O’Hara.
Property from Leigh’s two homes, Notley Abbey and Durham Cottage, will also be sold, including the porcelain, silver and glassware which Leigh and Olivier used to entertain guests.
Leigh’s 19th Century dressing table (£900) and books from the couple’s library are among the highlights.
Leigh’s pink, full length, evening dress is expected to fetch up to £300 and a diamond bow pendant could reach £35,000.
Leigh’s wig for her role as Southern belle Blanche DuBois in A Streetcar Named Desire, for which she won her second best actress Oscar, could fetch £600.
A Gone With The Wind film script, presented to the actress by members of the cast, could sell for more than £3,500.
Sotheby’s UK chairman Harry Dalmeny said the auction provided the chance “to discover the real, and unexpected Vivien Leigh”.
“We’re all guilty of.... blurring Vivien’s identity with that of Scarlet O’Hara or Blanche DuBois,” he said.
“But behind the guise of the most glamorous and talked-about woman of her age, we find a fine art collector, patron, even a book worm, who was the intellectual equal of the literati, artists and aesthetes she counted among her coterie.
“Her private collection does not disappoint. Vivien approached the decoration of her homes as if she were designing a set, incorporating influences and inspiration from a life spent on screen and on stage.
“These houses were an extension of the theatrical space, with medieval Notley Abbey looking positively Shakespearean.
“Fifty years on from her death, this sale opens the door into Vivien’s private world, allowing us a ... fascinating glimpse into a world that otherwise only her closest friends could ever have known.”
Leigh died in 1967, aged just 53, in London, after suffering from tuberculosis.
:: The auction will take place at Sotheby’s in London on September 26.