Maybe, but I'm sure Her Majesty's servants would never admit that. Actually, an air gun dealer claims the Walther LP53 air pistol was used for the 007 promotional portrait because it looked cool (which it does), while a reader asserts that Connery "attended the photo shoot for the film, but he did not have the original gun with him. He was loaned an air pistol belonging to one of the photo shoot people."
Looks a bit like a Colt Woodsman.