Alex Salmond will attend the Accession Council after a top official in his Alba Party called for an end to the monarchy in Scotland after the death of the Queen.
The Alba leader revealed he will be among 200 privy counsellors to attend the accession of King Charles.
He is one of the hundreds of members of the Privy Council.
It comes after Alba General Secretary Chris McEleny said there was “no place” for King Charles in an independent Scotland.
Scotland's First Minister Nicola Sturgeon will also be an eyewitness to event at St James's Palace in London which is due to take place at 10am.
The Accession Council is usually convened within 24 hours of the death of a monarch, but it has been delayed after the death of Queen Elizabeth was not announced until the evening on Thursday.
It is divided into two parts, with the first part seeing the Privy Council proclaim the Sovereign and the second part seeing King Charles III hold his first Privy Council.
After confirming his attendance, Mr Salmond referred to the new monarch swearing an oath to uphold the Claim of Right of 1689 during the Privy Council as the "sort of history which can shape the future".
In the second part of the Accession Council, King Charles will read and sign an oath to uphold the security of the Church in Scotland.
Mr Salmond tweeted: "In Part II of the Council, the new King is required to swear an oath to uphold the separation of church and state in Scotland, in accordance with the Claim of Right
"The Claim of Right of 1689 is not the bee’s knees in many quarters because of its 17th century anti-Catholicism, and very understandably so. But the idea of a contractual monarchy was first introduced into Scottish thought in the 14th century appeals to the Avignon Papacy.
"And the high principles of equality in the American Declaration of Independence, co-existed with the evil of slavery for the best part of a century - but these principles of equality were still well worth saying.
He said the Act is "properly seen as part of a golden thread of Scottish constitutional thought stretching from the Arbroath Declaration to the present day".
He concluded: "In any event, it can hardly be argued that the Claim of Right is merely a historical curiosity, when one of the first acts of the new King is to be required to swear an oath to uphold it! This is the sort of history which can shape the future."
His attendance follows a strongly worded statement from Alba Party's Mr McEleny.
“The very idea of retaining the monarchy in an independent Scotland to allow Charles, the Duke of Rothesay, to be our constitutional Head of State would be the antithesis of actual independence for Scotland," he wrote.
Although traditionally all 700 privy counsellors would attend, this Accession Council has been dramatically scaled down to a lack of space and concerns over safety.
Some senior politicians and members of the celery have been priorities with the remaining 500 being balloted for a chance at a seat.
Former first minister of Scotland, Jack McConnell, was one of the politicians who did not amanage to snag a seat.
He tweeted: "Best wishes to all my fellow Privy Counsellors who were successful in the ballot to attend this morning’s Proclamation of King Charles III. A rare historical moment. Meanwhile, it’s the [train] to [Scotland] for me."
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