Expected to raise more than pounds 250,000, the sale encompasses the novelist's entire career, from contributions to his school magazine in 1922 to the unfinished novel he gave away weeks before his death in 1991.
Formed by the American real-estate dealer Clinton Ives Smullyan Jr, the archive is of special interest because it covers so many aspects of Greene's life: from his miserable schooldays as the headmaster's son at Berkhamsted, to his time at Oxford - where he got a taste for Russian Roulette - and his work as a spy for MI6 in the Second World War.
He began spying under the command of the double agent Kim Philby, who later defected to the Soviet Union. Greene was put in charge of the writer and television personality Malcolm Muggeridge.
His biographer Norman Sherry observed: "By nature he was the perfect spy; he was an intensely secretive man."
The theme of betrayal and espionage, beginning with his early betrayal of a schoolmate to his father, and reinforced by the work for MI6, fascinated Greene, who was frequently unfaithful to his wife Vivien before, without warning, he left her.
Included in the sale at Sotheby's on 16 December is Greene's annotated copy of Andrew Boyle's The Climate of Treason (which is expected to fetch up to pounds 1,500). Greene's notes reveal his opposition to the view of Philby as an amoral traitor.
At one point, the book quotes Muggeridge as saying that Philby admired Goebbels, the Nazi propaganda minister, and wanted to work for him. "Nonsense." Greene wrote crossly in the margin. "Typical of MM."
Later, Boyle wrote of the "treacherous lengths to which the Soviet Union and its hidden accomplices [are] prepared to go". "How can one apply morality in these realms?" Greene scribbled.
As a student at Oxford, the novelist was briefly a member of the British Communist Party, which caused him problems getting US visas and resulted in the FBI opening a file on him.
While writing an article for The Spectator, Greene applied for the release of their documents under the Freedom of Information Act. He was sent a heavily censored set of photocopies which are estimated to fetch up to pounds 4,500.
Another important lot is Greene's proof copy of the novel many consider his masterpiece, The End of the Affair. Estimated at up to pounds 9,000, it contains both Greene's corrections - in blue ink - and those of Evelyn Waugh, in red. Greene asked his fellow writer for comments when he realised the sensation that his story about a wartime love affair might cause.
The copy reveals that Waugh, whose writing was also bound up with Catholicism, was cautious about some of Greene's allusions. He queries a number of passages including the comparison of a man to an "abortion".
A series of letters from Greene to his great protege, the novelist R K Narayan, is also up for sale, as is Greene's proof copy of The Heart of the Matter - littered with his corrections - and his annotated script of The Third Man, the film which starred Orson Welles.
"One of the nicest things about the sale," said Peter Selley, the specialist in charge of the auction, "is that it includes books with inscriptions from Graham to the great love of his life, Catherine Walston, his first mistress, Dorothy Glover - one of which says `from Graham Greene the bastard' - and to his wife, Vivien, who brought up their children."