But the SNP leader said he told Connery that Mr Dewar was "a straight and decent man" and would carry through whatever was agreed at a secret lunch between the trio.
The outgoing party leader said Mr Mandelson made the approach without the knowledge of the then Scottish Secretary Donald Dewar.
In a memoir serialised in the Scotland on Sunday newspaper, Mr Salmond said the Labour MP, who is now Northern Ireland Minister, wanted to bring in the former James Bond star because of concerns that the campaign for a yes vote was flagging.
"It was, and remains, my distinct impression that Mandelson kept Dewar out of the loop while the first contact was made, only enlightening the man who was supposed to be running the campaign once the deal was done," said Mr Salmond.
But the SNP leader said he told Connery that Mr Dewar was "a straight and decent man" and would carry through whatever was agreed at a secret lunch between the trio.
"The following year I was to regret these remarks when I discovered that Dewar had so callously knifed Connery in the back over his knighthood," said Mr Salmond.
The SNP supporter, who celebrated his 70th birthday last month, was finally knighted by the Queen in July this year.
Mr Salmond is stepping down as SNP leader after 10 years, with his swansong coming at the party conference in Inverness later this month.
Mr Salmond said that Mr Mandelson, who was at the time minister without portfolio with a "licence to dabble" in all areas of government, was worried that Labour's devolution referendum campaign had lost impetus.
"Mandelson's solution was to speak to Connery, instantly identifiable as the world's most famous living Scotsman, and tell him he was needed to give the campaign a fresh impetus that would capture the public imagination," said Mr Salmond.
'In the dark'
He believed Mr Dewar, who had an "innate hostility" towards nationalism, "must have been in the dark" about the approach.
The 007 star expressed his fears about being used as a political trophy in a phone call to Mr Salmond.
Connery wanted a face-to-face meeting with Mr Dewar "because that is his way of deciding if he can trust people".
The lunch, which Mr Mandelson did not attend, took place in August 1997 in a private room at a London restaurant.
Mr Salmond claimed Mr Dewar "seemed
to be starstruck for the first five minutes" before they started the serious political discussions.
The initial plan for a series of events featuring Connery was shelved when the death of Princes Diana led to a moratorium on political campaigning, meaning that the actor's involement was crammed into one day.
"As chance would have it, this change of tactics had the effect of endowing Connery's contribution with even more dramatic impact that he might otherwise have achieved," said Mr Salmond.
"Looking back, it doesn't seem credible that one man, even Sean Connery, made the difference between success and failure given the eventual comfortable margin of victory for the Yes-Yes campaign.
"However 'Connery Day' was immensely important. It set the tone for the final few days of campaigning where the Yes-yes camp were totally dominant and the No-No rivals were blown away completely."
Claims that Mr Mandelson personally asked Connery to join the campaign were raised a year ago by Mr Salmond's biographer Alan Taylor.
He also told the Edinburgh International Book Festival that Connery and Mr Salmond remained bitter about Labour's treatment of the star, who was initially refused a knighthood.
Full independence
Writing in Scotland on Sunday, Mr Salmond also revealed that he could have asked Mr Dewar to give the Scotish Parliament further powers.
But he said Mr Dewar "could never offer anything approaching the independence the SNP desired.
"Therefore any concession offered would be, by definition, inadequate from an SNP viewpoint."
Instead he asked his Labour counterpart to concede in parliament that Westnminster would not stand in the way of full independence if that was the will of the people.
A spokesman for the Scottish Labour Party described Mr Salmond's claims as "old hat and rather sad, tired rubbish".