The Christian Aid event in St Andrew's and St George's West Church, George Street, which has raised nearly 2 million over the years, will this year feature lots to coincide with the 150th anniversary of JM Barrie's birth.
Organisers have gathered together a special collection of Peter Pan memorabilia, including a set of postcards from 1906-7, showing actresses as Peter in the first productions of the play, which premiered in 1904.
The sale's organiser, Mary Davidson, 72, said: "I was born in the year JM Barrie died and all girls my age had an edition of Peter Pan. This is a lovely way to celebrate his life and it is such a worthy cause."
Other items at the sale, which every year sells pieces to the British Library and National Library of Scotland, include a 1748 copy of philosopher John Locke's Essay Concerning Human Understanding.
There is also a rare 1887 collection of Hans Christian Andersen fairy stories, featuring the Ugly Duckling and Snow Queen alongside little-known tales like The Beetle Who Went on his Travels, Soup from a Sausage Skewer and The Galoshes of Fortune.
But one of the highest prices will be for Tour of Scotland, written by English adventurer Thomas Pennant in 1776.
The chapter on Edinburgh, penned in 1769, reads: "The view of the houses at a distance strikes the traveller with wonder; their own loftiness, improved by their almost aerial situation, gives them a look of magnificence not to be found in any other part of Great Britain."
Dr Reid Zulager, 46, has a PhD in Scottish literature and history from the University of Edinburgh and travels from his Washington DC home every year to help with the sale. He said: "The tour guide will fetch hundreds of pounds. It is so detailed, it's as if you could read the book instead of travelling there.
"This is the sort of attention to detail which makes us different from most charity sales. We get gifts of very unusual and fine things."
A friend asked Mrs Davidson to sell books for Christian Aid week in 1974, where she made 800. Now she accepts donations at her city centre home all year round, even at Christmas.
"It was Boxing Day and we had 19 people round the table," she said. "I departed because someone had new books for me, and I didn't regret it."
The sale will be on 8 May from 10am-4pm and 10-14 May, 10am-3:30pm. Doors will stay open until 7pm on 13 May.