The high-profile diplomatic team hopes to bring to the table the voice of a continent that has been badly hit by rising grain prices and the wider impact on global trade since Russia invaded Ukraine last year.
They will be seeking to persuade the two countries to end the war.
Reports of explosions and sirens howling Ukraine's capital have since been dispelled.
“It is very strange that we didn't hear or see an explosion. There's obviously some deliberate misinformation being spread here. People are going on about their day,” Ramaphosa’s spokesman said.
Last week, Ramaphosa spoke with Russian counterpart Vladimir Putin over the phone and briefed him about the “African leaders’ peace mission”.
“President Putin has welcomed the initiative by African heads of state and expressed his desire to receive the peace mission,” a statement from his office read.
Ramaphosa said he held separate phone calls with Putin and Zelenskyy who agreed to host the African leaders in Moscow and Kyiv to discuss the peace plan.
According to Ramaphosa, the conflict between the two countries has been devastating and African countries have borne the brunt.
The continent which relies heavily on imports from the countries has been hard hit especially due to the increase in the prices of cereals.
The head of state who initiated the process said their mission is a "mission of peace" and will be seeking to secure a commitment from both sides to end the fighting.
"The Russian and Ukrainian leaders must explain to us their point of view on the war as well as their minimum requirements to end the conflict," he stated.
