The 1926 copy of Television is signed by the inventor of television itself, John Logie Baird.
It was handed in to the Oxfam shop in Morningside and experts say it could be Baird's own copy.
The signature is on the blank half-title page, rather than the title page or frontispiece, which is where valuers would expect to see an autograph.
The book gives a brief history of TV up to that date, and ends with a detailed explanation of Baird's work and inventions, including an account of the first public demonstration of moving silhouettes he gave at Selfridges in March 1925.
The book, valued at between 800 and 1,000, will be sold by Bonhams auctioneers this month.
Andy Crosby, manager of Oxfam's Morningside bookshop, said: "One of our volunteers found the book and when I saw the signature inside it, it was one of those moments where I had to check that my eyes weren't playing tricks on me.
"We thought at first it was just a regular sort of signed copy, but, when we took the book to Bonhams, they said it was more likely to have belonged to Baird himself because of the location of the inscription, so that makes it a pretty special donation.
"I don't know whether the person who brought this book in was aware that there was a signature inside it, but I'd like to say a really big thank you to them for donating it to Oxfam."
John Logie Baird was born in Helensburgh in 1888 and went on to study at Glasgow University. He died in Bexhill-on-Sea, in East Sussex, in 1946.