The state visit will be Xi's second international trip of 2023, after making an official trip to Russia in March.
"Chinese President Xi Jinping left Beijing on Monday for the 15th BRICS Summit to be held in Johannesburg, South Africa, and a state visit to South Africa," Xinhua news agency reported.
The heads of Brazil, China, India and South Africa plus Russia's top diplomat will gather from Tuesday to Thursday this week under the theme "BRICS and Africa", South Africa's Foreign Minister Naledi Pandor said this month.
Questions had swirled over whether Russian President Vladimir Putin -- who is sought by the International Criminal Court (ICC) for his role in the Ukraine war -- would attend this year's BRICS conference in South Africa, which is a signatory of the ICC.
The Chinese leader previously visited South Africa in 2018 as he sought to enhance his country's diplomatic and economic ties with the continent.
On the agenda at this year's summit will be the possible future expansion of BRICS membership, which the bloc has previously indicated it is open to.
Several African countries have previously expressed a desire to join the bloc, including Algeria, Egypt and Ethiopia.
A total of 69 countries have been invited to the summit, including all African states.
BRICS, a loosely-defined group that sees itself as a counterweight to Western economic domination, derives its name from Brazil, Russia, India, China and South Africa.
The group represents 23 percent of the world's gross domestic product and 42 percent of the world's population.
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