The collection going under the hammer at Bloomsbury auction house, on October 3, includes four scarves and neckerchiefs owned by Orwell and is expected to fetch up to 1,200 pounds.
Orwell was wearing one of the scarves, with anti-fascist images and colours, when he was shot in the neck by a sniper during a battle near Barcelona in the Spanish Civil War in May 1937.
Although Orwell survived the neck wound, it ultimately contributed to his early death, 13 years later, 'BBC News' reported.
Writing in his Homage to Catalonia, Orwell's personal account of the war, he said he had been "about 10 days at the front when it happened".
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He continued: "Webb, our stretcher-bearer, had brought a bandage and one of the little bottles of alcohol they gave us for field-dressings. The doctor re-bandaged the wound, gave me a shot of morphine, and sent me off."
The scarves were saved by Hugh Patrick O'Hare, who treated Orwell in the aftermath of the shooting and was a fellow member of the Independent Labour Party (ILP).
Max Hasler, of auctioneers Bloomsbury, said that Orwellian memorabilia was rare but "to have something that relates to such a significant part of his life is especially unusual".
"I think it is a really interesting item. George Orwell was such a private person, very few examples of his signatures and photographs exist," Hasler said.