The King will host his first state visit as monarch from the President and First Lady of South Africa.
President Cyril Ramaphosa, accompanied by First Lady Tshepo Motsepe, has accepted the invitation to attend Buckingham Palace in November.
It is understood the visit was in the early stages of being planned before the Queen’s death in September.
The King has visited South Africa on a number of occasions since his first tour of the country, which included Pretoria, Johannesburg, Durban and Cape Town, in 1997.
His last trip was in 2011, when along with the Queen Consort, then the Duchess of Cornwall, he carried out engagements including a speech on climate change at the University of Cape Town and a visit to the Black Rhino Range expansion project in Phinda Game Reserve.
They also attended the Nelson Mandela Foundation, where they were received by Graca Machel, the former president’s widow.
Charles was also present at Mr Mandela’s funeral in 2013, remarking the world would be a “poorer place without him” and that he was owed “an enormous debt of gratitude for what he’s managed to achieve with his life”.
The King and the Queen Consort, then the Prince of Wales and Duchess of Cornwall, also welcomed President Jacob Zuma at the start of a state visit in the UK in 2010.
Mr Ramaphosa’s visit will take place from Tuesday November 22 to Thursday November 24 and be hosted by the King and Queen Consort at Buckingham Palace.
It comes as Mr Ramaphosa faces allegations of money laundering that threaten his position at the heart of Africa’s most developed economy.
The president has denied the accusations, which include illegally holding around four million dollars in cash at his game ranch in northern South Africa and covering up its theft in an attempt to hide the existence of the money.