Only 30 bottles of Big Tam’s Ale were made to mark the awarding of a knighthood to Sir Sean 14 years ago.
The Scottish & Newcastle beer comes complete with a picture of the actor on the label.
There is little precedence for such sales and estimates of its worth range from as little as £2 to “priceless”.
However, the bottle should fetch at least £100 and, if Bond fans get into a bidding war, it could go for a four figure sum.
The bottle “Big Tam’s Ale” was presented to Sir Sean on July 5, 2000 at a gathering in the City Chambers to mark his Knighthood, conferred on him by the Queen, at the Palace of Holyroodhouse.
The limited run of bottles is said to have been made on the instructions of the then Scottish & Newcastle Chief Executive Brian Stewart.
The bottle says “Sir Sean Connery, Palace of Holyrood House” and has a grinning Sir Sean on the label, replacing the historic Laughing Cavalier mascot.
It also celebrates Connery’s 70th birthday the following month by stating “1930 - 2000: From one Fountainbridge Legend To Another”.
Sir Sean was joined by his wife Micheline at the event which was arranged by former Edinburgh City Lord Provost, Cllr Eric Milligan.
The bottle has been donated by Edinburgh businessman Grant MacDonald, who was given the bottle by Sir David Murray who attended the event, with all funds raised going to Pancreatic Cancer Action UK.
John Martin, Chairman of the Scottish Brewing Association, who previously worked at Scottish & Newcastle, and has a bottle of the special edition beer said: “A collector could pay a high amount of money for something like this. It’s a collectors item.
“If you got two people together who really wanted it you could get a high value. I’ve never seen any go on the market.
“I remember Sir Sean came to Edinburgh and Scottish & Newcastle and we made a small film of him leaning out the tenament building where he lived looking across at the Fountainbrigde brewery and where he used to do his milk run,” he added.
Mike Peterson, a UK based beer collector and seller said: “If purchased by a collector, the bottle would probably sell for the label or the cap, as there are more label and cap collectors than full bottled beer collectors. I think around the year 2,000 McEwans used a fairly unusual cap, especially on their Parliament Ale, which this is a relabelled example of.
Matteo Menestrina from online auction site just-whisky.co.uk said: “We normally deal in high end whisky, but when we saw the uniqueness of this bottle - and the fact it was for charity - then we were delighted to help.
“This is a very rare bottle and will be a big hit with Bond fans and those into rare bottles, so we hope it will raise some good money for a very worthwhile charity.”
Ali Stunt, CEO of Pancreatic Cancer Action, said: “We are delighted that someone is kindly auctioning off this special edition beer to support us. As a charity, we rely on the generosity of individuals to help us continue our vital work. We wish them lots of success with the auction.”
The online auction starts this Friday and biddings will close on October 19.