The early edition of Fleming's first novel, Casino Royale, has an inscription from the author which reads: "Alastair, from the Author, Read & Burn".
Published in 1953, when Fleming was 44-years-old, it was the first introduction to legendary spy 007.
Inside the dust-jacket of the book, which is estimated to fetch between £12,000 to £18,000 at auction, is written: "Ian Fleming is 44.
"Like his brother Peter, the more famous author, he was educated at Eton."
Fleming, known around the world for his James Bond series, wrote twelve novels, and two collections of short stories, inspiring a franchise of 26 films to date.
First editions of Fleming's Bond novels are highly sought after, particularly those published in the 1950s, prior to the first James Bond film release, Dr. No, in 1962.
Others up for auction include Live and Let Die, Diamonds are Forever and The Man with the Golden Gun, all of which are expected to sell for between £1,000 and £5,000.
The titles will go under the hammer at Lyon & Turnbull in Edinburgh on October 9.
Born in 1908, Ian Fleming spent his early years at Eton, Berkshire, before moving to the Royal Military Academy at Sandhurst, Surrey.
In 1931 he joined Reuters but it was during World War II that Fleming began to gather his insider knowledge of secret operations as personal assistant to the Director of Naval Intelligence at the Admiralty.
After the war, Fleming began to develop his Bond stories from his house, Goldeneye, in Jamaica.
Over the next decade, more than 40 million copies of Bond's adventures were sold - cementing James Bond as one of the 20th century's greatest fictional works.
Cathy Marsden, a book specialist at Lyon & Turnbull, said: "We've had first edition copies of the later ones, published in the 1960s, and we've sold Casino Royale and Live and Let Die before but they don't come in often.
"James Bond books are selling quite well at the moment, people seem keen to get their hands on them.
"Live and Let Die is in very nice condition and Casino Royale is in good condition apart from a stain on the back cover.
"The work was published in a run of just over 4,500 copies - a figure which seems large but pales in comparison to the posthumously published The Man With the Golden Gun, which commanded a print run of 82,000 copies.
"Today, first edition copies of Casino Royale complete with dust-jacket are relatively rare - inscribed copies are even more unusual.
"It's pretty vital as they'd be worth a lot less without the dust-jackets."