The book, dated 1925, is inscribed with a dedication to Georg Maurer, whom Adolf Hitler met in Landsberg Prison in Germany while serving a sentence for treason after the failed 1923 Beer Hall Putsch uprising in Munich.
Hitler wrote "Mein Kampf" - which means "My Struggle" in English - while serving his sentence at Landsberg. He originally wanted to call it "Four And A Half Years Of Struggle Against Lies, Stupidity And Cowardice."
Maurer was a local Nazi official incarcerated at the same time who later fell out with Hitler after giving a list of Nazi supporters to a Marxist newspaper.
Initially, "Mein Kampf," which outlines Hitler's extreme anti-Semitic ideology, had a small print run but during his time as German leader from 1933 to 1945, it was enormously popular.
The book was even given out free to newlywed couples in Nazi Germany.
Richard Westwood-Brookes of auctioneers Mullocks, who are selling volume one of the work at Ludlow in western England, said it was "very, very, very rare," adding he had had interest from as far afield as Russia and the United States.
"There's this incredible interest in Hitler," he told AFP. "The bad boys in history are always the ones that people get really interested in."
Mullocks are selling the copy of "Mein Kampf" alongside a signed self-portrait of Hitler found by a British soldier in the house of a wealthy Nazi in Cologne in 1945 as he and other troops patrolled the city.
The self-portrait, which is in pencil and dated 1926, is also expected to sell for up to 20,000 pounds.