The three volume presentation copy is the only one from the original print run of 12 known to exist today.
The literary legend requested that 11 of the books went to members of the Royal family, including the Prince Regent, and her own family, the Daily Mail reported.
The one that has now emerged for sale was gifted to Anne Sharp, a close friend of the novelist.
A clerk at the publishers was specifically instructed by Austen to pen the words 'from the author' on the title page of the book, which is still present today.
'Emma' was the last of Austen's work to be published while she was alive and followed her other classics Sense and Sensibility, Pride and Prejudice and Mansfield Park. It tells the tale of the misadventures of matchmaker Emma Woodhouse.
"Jane Austen contacted her publishers and asked for 12 copies of her new novel to go to various people. These people were either royalty, members of her family and friends," Dr Philip Errington, a specialist in English literature at auctioneers Sotheby's, said.
"But just one copy went to a friend and that was Anne Sharp, who was the governess at the school of Austen's niece Fanny Knight," Errington said.
"It is not known what happened to the 11 other books and this is the only one of the 12 to come on the market before Jane Austen wasn't a celebrity or personality so there was little need for her to sign copies of her work," Errington added.
"Its rarity and the fact there is a direct link between the owner and the author gives it its value," Errington said.
The novel has been in the hands of a private collector for many years.
It will be sold at Sotheby's in London on December 12.
