Sinn Fein requested the meeting between Prince Charles and Gerry Adams ITV News understands.
Although the Prince has previously met Martin McGuiness, today will be the first time he has met the President of Sinn Fein.
The Prince of Wales is making an historic trip to the west of Ireland where his great uncle Lord Louis Mountbatten was assassinated by the IRA.
The great-uncle of Prince Charles was killed along with his 14-year-old grandson and two others in an IRA bomb blast in August 1979.Read the full story ›
An anticipated historic meeting between Sinn Fein leader Gerry Adams and Prince Charles has been hailed in some quarters as the next phase in deepening the bonds between the UK and Ireland.
The meeting with Mr Adams will take place before Prince Charles visits the site of his great-uncle Lord Louis Mountbatten's murder and is a way of "promoting reconciliation and healing", according to a Sinn Fein party official.
Lord Mountbatten was assassinated by the IRA along with Lady Doreen Brabourne, the 83-year-old mother-in-law of the earl's daughter, his 14-year-old grandson Nicholas Knatchbull and 14-year-old Paul Maxwell, from Killynur, Enniskillen in 1979.
Sinn Fein leader Gerry Adams is expected to meet Prince Charles in what would be an historic meeting in Ireland. It is understood that Mr Adams is among guests expected to meet the Prince tomorrow as he begins his four-day tour of Ireland.
The Prince of Wales begins an emotional and historic trip to the west of Ireland where his great uncle Lord Louis Mountbatten was assassinated by the IRA. One of the most poignants stops on the official four day visit to the Republic and Northern Ireland will be on Wednesday when Prince Charles arrives in Mullaghmore, Co Sligo, the site of the atrocity.
All of Ireland's main political leaders have been invited to National University Ireland Galway but the prospect of the visit beginning with the first meeting of a royal and a Sinn Fein leader in the Irish Republic will undoubtedly set the tone.
Sinn Fein president Gerry Adams has confirmed his party will attend some events when the Prince of Wales visits Ireland for four days this week.
The move was widely expected given the recent thawing in relations between the republican party and the Royals, beginning with the Queen's historic handshake with former IRA commander Martin McGuinness in Belfast in 2012.
Mr Adams said his party's governing Ard Chomhairle had agreed that representatives should attend events which will see Charles and the Duchess of Cornwall fulfil engagements on both sides of the border.
This week's Royal visit will provide another highly symbolic moment when Charles visits the scene of Lord Mountbatten's murder by the IRA in 1979.
The Royal couple will tour Mullaghmore in Co Sligo where his great-uncle and godfather was killed by a booby trap bomb while on a fishing holiday.
Prince Charles is the Colonel-in-Chief of the Parachute Regiment. A regiment of the British Army that has been responsible for killing of many Irish citizens...
But he also has been bereaved by the actions of republicans. Thankfully the conflict is over. But there remains unresolved injustices. These must be rectified and a healing process developed.
There is a responsibility on us all to promote reconciliation and seek to promote healing.
Members of the public have told ITV News they find Prince Charles' letters to MPs "helpful and sensible" and said "there's nothing wrong in what he's done at all".
For many people, it is not whether the monarch has the right to express his opinions, but if he should be allowed to influence government decisions.
ITV News Correspondent Damon Green reports:
David Cameron says he has had "relatively regular" meetings and correspondence with Prince Charles, adding: "I think the heir to the throne should have every right to write letters to government ministers or politicians."
Speaking to ITV Wales News, the Prime Minister described the Prince of Wales as a "man with huge passion about public life" and said "I hope he carries on having the strong views that he does".
He also said his government had made the "right" decision in amending the Freedom of Information Act to prevent future correspondence between the monarch and heirs to the throne being published.
From the fate of the Patagonian Toothfish to preserving the memory of some of Britain's greatest explorers, Prince Charles touched upon a great number of varied issues in his now-public letters to Government ministers.
Lawmakers have taken the threat of today's publication seriously enough to amend the law around the Freedom of Information Act so correspondence from the monarch and the heir to the throne cannot be released in future.
ITV News Correspondent Paul Davies reports on the release of the memos - a culmination of a ten-year legal battle.
Prince Charles faces accusations of interference with government affairs after letters made public today showed him raising concerns on a number of issues with ministers, including Tony Blair.
Among the issues raised was an alleged lack of resources for troops on the front line in Iraq, as ITV News Royal Editor Tim Ewart reports.
A summary of the Prince of Wales' correspondence with ministers, which was released today after a ten-year legal battle.Read the full story ›