Sean loses licence to thrill the Queen.
The Scottish actor has been excluded from a gathering of the best of Britain's film and arts world at a reception in the newly-restored Windsor Castle, which will be attended by the Queen.
The Scottish Office excluded the 007 star from a list of Scotland's best-known actors to be sent invitations to the reception on April 29.
Among those invited and who will be presented to the Queen include Billy Connolly, Full Monty star Robert Carlyle, Trainspotting's Ewan McGregor, Cracker star Robbie Coltrane and Four Weddings and a Funeral actor John Hannah.
The new row comes just weeks after the disclosure that Connery was denied a knighthood by Scottish Secretary Donald Dewar.
His name had originally been put forward by former Tory Scottish Secretary Michael Forsyth.
It was claimed the honour was denied because of the Bond actor's remarks on violence towards women.
However, it is widely believed the decision was taken on political grounds as Connery is a high-profile supporter of the Scottish National Party.
Last September he took part in the Scotland Forward campaign for a devolved Scottish Parliament - standing on the same platform as Mr Dewar. He has also met the Prime Minister and Chancellor Gordon Brown to discuss tax incentives to create a competitive British film industry.
SNP leader Alex Salmond said the latest revelation proved that Scottish Office ministers are "intent on persistent persecution of Sean Connery."
"It is high time they ended this insulting and petty vendetta which has caused so much damage to the reputation of Donald Dewar and the Scottish Office," he said.
"I would have thought they should have realised by now that the more they attack Connery the further they fall in public esteem in Scotland.
"I doubt very much if Sean will be too bothered by not getting invitations to their parties, but this occasion shows up the Scottish Office for the smalinded individuals they are."
The damage done to the Government by snubbing Connery, along with other perceived gaffes, resulted in a shock poll which put the SNP just one percentage point behind Labour in current voting intentions for the Scottish Parliament.
Buckingham Palace said the reception was one of many in which Government departments were approached to help advise on invitations.