Ross, who was , has selected the Jon Ronson title as his first choice of book.
Ross revealed the idea for his bookclub last week on his Twitter account, twitter.com/wossy, which has 272,531 followers.
Last Friday he posted the tweet: "I have a great idea! Let's start a book club on Twitter! One a week and we all post mini-reviews!"
Ronson's book was nominated as the first to be review.
The timing of this Sunday's online book club (which can be followed at @atwossybookclub via Twitter) coincides with the launch of the digital version of the book by Exact Editions.
The company, which works with publishers to sell readers digital versions of their content, has gained the rights to sell the Ronson book digitally.
, where users can read the contents page and first chapter; or pay £4.99 for subscription to read the book in full.
However, on Sunday between 5pm and 6pm (when Ross's club is live), the book will be available for free in its entirety, so that members of Ross's book club can access it in full.
Daryl Rayner, managing director of Exact Editions, said: "We are delighted to be working with Pan Macmillan on the launch of the digital edition of 'The Men Who Stare at Goats'.
"Given the online environment of the @atwossybookclub it makes absolute sense for the Twitterati to be given the opportunity to link to the web pages they are discussing in their tweets."
Sara Lloyd, digital director of Pan Macmillan, said: "Jonathan Ross made the sudden announcement that 'The Men Who Stare at Goats' was to be his first book club pick just a few days ago.
"Since then there has been great interest in the title and we are thrilled to be able to offer it as a digital version through the Exact Editions platform."
'The Men Who Stare At Goats' examines some of the ludicrous beliefs and practises at the heart of American's 'War on Terror'.
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