A freedom of information request revealed that the First Minister sent the SNP's most prominent supporter a Sandi Thom CD and an autographed copy of the Scottish Government's white paper on independence among four letters.
They confirm a close friendship between the politician and the James Bond star which has apparently spilled over from the golf course into Mr Salmond's job as First Minister.
The correspondence, sent at the taxpayers' expense, all went to Sir Sean's tax haven in the Bahamas and has been branded "bizarre and deeply, deeply embarrassing" by Labour.
It also revealed the starry-eyed Mr Salmond played secretary to the Hollywood icon, forwarding him scripts and fan mail sent to the Scottish Government.
The first letter, sent on official headed paper last January, reads: "Dear Sir Sean, Sandi Thom has very kindly sent me an advance copy of her new album which will be released in the spring.
"Sandi played at the St Andrew's Day celebrations in Edinburgh to great acclaim, despite the fact her mother had been taken ill on the same day.
"I have greatly enjoyed listening to Sandi's album, so I am forwarding it to you in the hope that you will, too."
The letter also contained a DVD of the presentations made for Glasgow's bid for the 2014 Commonwealth Games and a BBC Scotland compilation DVD. It is signed off: "Best wishes for 2008 to Micheline and yourself. Yours for Scotland, Alex."
Another letter, also sent in January, included a signed copy of the SNP's white paper on independence as a gift.
The letter, signed by correspondence secretary Michael Birrell, read: "The First Minister has asked me to apologise for the delay in sending this to you."
A further letter included scripts from Scottish playwright James Duthie.
The letters have been derided by political opponents, who have questioned whether this was a good use of the First Minister's time and of public money.
A spokesman for the Scottish Labour Party said Mr Salmond's behaviour was "inappropriate". He said: "This bizarre correspondence with Sean Connery is deeply, deeply embarrassing for Mr Salmond.
"He should be doing his job – not swapping records and videos with SNP supporters in offshore tax havens."
The spokesman added: "The irony of signing a copy of a white paper on separation – as opposed to an act of parliament – appears to be entirely lost on the First Minister. It shows he is a talker, not a doer." But a spokesman for Mr Salmond said his critics were jealous of his relationship with the star. He branded Labour's attack a "weird rant".
He said: "Sean Connery is one of the most prominent Scots in the world – the fact that he featured in the successful Commonwealth Games presentation in Sri Lanka was an enormous asset for Glasgow and Scotland, as indeed is his prominent role in the Homecoming campaign at present.
"Labour should take a long, hard look at themselves, because when all this positive work is going on they come across as small-minded and jealous."
Aberdeenshire-born Thom, 27, is a vocal supporter of the SNP and features on the party's website. She also appeared alongside Sir Sean in a recent advertisement for Homecoming Scotland, singing the Dougie McLean song Caledonia.
THERE is nothing in the ministerial code to prevent the First Minister or any other minister from engaging in correspondence with individuals or organisations.
The only restrictions concern letters and relationships that affect ministerial decisions.
In particular ministers have to be careful concerning planning decisions, although they can make representations on behalf of their constituents as long as they are removed from making any decisions.
This was the basis of the last major controversy surrounding Alex Salmond when he met and corresponded with Donald Trump's representatives for a golf resort application in his Gordon constituency. However, even though Sir Sean Connery is a personal friend of Mr Salmond's, the First Minister could argue that correspondence with one of the world's most famous Scots, who participates in Scottish Government activities such as the Homecoming campaign, is legitimate business.
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