The meeting in Johannesburg this week of BRICS nations -- Brazil, Russia, India, China and South Africa -- will seek to widen their influence and push for a shift in global geopolitics.
South Africa's hosting of the summit has turned a spotlight on its ties with the Kremlin, especially as it has refused to condemn Russia's invasion of Ukraine.
"While some of our detractors prefer overt support for their political and ideological choices, we will not be drawn into a contest between global powers," Ramaphosa said in a televised state of the nation address.
"We have resisted pressure to align ourselves with any one of the global powers or with influential blocs of nations," he said.
Ramaphosa will be joined at the BRICS summit by China's President Xi Jinping, India's Prime Minister Narendra Modi and Brazil's President Luiz Inacio Lula da Silva.
Russia will be represented by Foreign Minister Sergei Lavrov, with President Vladimir Putin participating online.
Putin decided against attending in person as he is the target of an International Criminal Court arrest warrant that South Africa is in theory bound to enforce.
Some 50 other leaders who are not BRICS members -- among them Iran's Ebrahim Raisi and Indonesia's President Joko Widodo -- have confirmed they will attend the talks.
The BRICS nations account for about a quarter of the global economy and interest in joining the group has surged this year.
At least 40 countries have shown interest in becoming members, with 23 having submitted their applications.
South Africa supports calls to open up membership of BRICS.
"An expanded BRICS will represent a diverse group of nations with different political systems that share a common desire to have a more balanced global order," said Ramaphosa.
Some of the countries aspiring to be BRICS members include Argentina, Bangladesh, Bahrain, Cuba, Ethiopia, Indonesia, Iran, Nigeria and Saudi Arabia.
Expansion plans were first mooted last year, according of South Africa's foreign minister Naledi Pandor.
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