Russian President Vladimir Putin and Ukrainian President Volodymyr Zelensky have "agreed to receive the mission and the African heads of state, in both Moscow and Kyiv," Ramaphosa said.
Ramaphosa said he had held "separate telephone calls" with Putin and Zelensky over the weekend, where he presented an initiative drawn up by Zambia, Senegal, the Republic of Congo, Uganda, Egypt and South Africa.
"I agreed with both President Putin and President Zelensky to commence with preparations for engagements with the African heads of state," Ramaphosa said.
"We're hoping we will have intensive discussions," he said, speaking at a press conference in Cape Town during a state visit by Singapore Prime Minister Lee Hsien Loong.
UN Secretary-General Antonio Guterres and the African Union (AU) have been briefed on the initiative and welcomed it, Ramaphosa added.
Ramaphosa did not give a specific timeline for the visit or other details, saying only that the conflict had been "devastating" and Africa "is also suffering a great deal" from it.
African countries have been badly hit by rising prices of grain and by the impact to world trade.
The announcement came a day after Ramaphosa said South Africa had been under "extraordinary pressure" to pick sides in the conflict, following accusations from the United States that Pretoria supplied weapons to Moscow -- a move that would break with its professed neutrality.
- 'Cautious support' -
The mission will be the latest in a flurry of so-far unsuccessful diplomatic efforts to still the war.
A Chinese special envoy was expected to arrive in Kyiv for a two-day visit on Tuesday to promote Beijing-led peace negotiations.
Last week Guterres told a Spanish newspaper that peace negotiations were "not possible at this moment" with both sides "convinced that they can win."
But Ramaphosa said the African initiative had met with "cautious support" in Washington and a number of European capitals visited by "facilitators" tasked with presenting the plan.
The effort could help Pretoria rehabilitate its image as a neutral player and mediator, following accusations that it has drifted towards Russia.
The commander of South Africa's ground forces was in Moscow to discuss military cooperation on Monday, in the latest of a series of incidents that critics cite as evidence of a tilt towards the Kremlin.
Last week, the US envoy to Pretoria said that the United States believed weapons and ammunition had been laden onto a Russian freighter that docked at a Cape Town naval base in December.
- Expletives and bubble-gum -
On Tuesday, South Africa's defence minister, Thandi Modise, denied the accusation in an interview with local newspaper the Mail & Guardian.
"Everybody now sees the spook called South Africa. I can tell you that categorically, we did not send fokol, not even a piece of Chappies to Russia," she said referring to a local popular bubble-gum brand and using an Afrikaans expletive meaning "nothing at all".
On Monday, Ramaphosa said South Africa would not be drawn "into a contest between global powers" despite having faced "extraordinary pressure" to do so.
South Africa has refused to condemn the conflict in Ukraine, which has largely isolated Moscow on the international stage, saying it wants to stay neutral.
In a veiled criticism of that stance on Tuesday, Singapore's Lee said condemning Russia's invasion was a matter of principle.
"One country cannot invade another with impunity...a clear disapproval has to be given," he told the press conference in Cape Town, flanked by Ramaphosa.
"We remain friends with Russia but we cannot approve of what has been done".
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