"I have indicated to the commission that I would be available to provide testimony," Ramaphosa said in a short statement issued Saturday evening.
"I believe there are a number of issues relevant to the deliberations of the inquiry on which I may be able to make a contribution."
Ramaphosa's role in the events leading up to the shooting of 34 striking Lonmin mineworkers on August 16 was discussed during the commission's hearings last week.
Advocate Dali Mpofu, representing the miners injured and arrested after the shooting, mentioned an e-mail in which Ramaphosa strongly condemned the protests, described them as criminal acts, and suggested "concomitant action".
Mpofu said there were e-mails sent between Lonmin management, government ministers and Ramaphosa.
The commission's brief is to investigate the shooting that left 34 miners dead when police tried to disperse them on August 16. The workers, who wanted monthly salaries of R12 500, had been carrying knobkerries, pangas, sticks, and iron rods.
Ramaphosa came in for a battering from the ANC Youth League and its expelled leader Julius Malema's "economic freedom fighters" on Wednesday.
The league called for his arrest after it was revealed – during the course of the Farlam commission into the Marikana killings – that Ramaphosa had sent emails to Lonmin management and government ministers asking for action against striking miners. It also used the opportunity to reiterate its calls for nationalisation of the mines.
But analysts say this is unsurprising given Ramaphosa's role in having Malema expelled from the ANC earlier this year.
Ramaphosa chaired the national disciplinary committee that expelled Malema and former league spokesperson Floyd Shivambu at the beginning of the year.
He is also rumoured to be a candidate for the number two spot on the Jacob Zuma faction's slate at the ANC's elective conference in Mangaung come December, while the youth league and Malema's allies have thrown their weight behind the opposing camp in favour of Kgalema Motlanthe.
Advocate Dali Mpofu, who represents some of the miners injured and arrested during the events at Marikana, revealed the contents of the emails during his opening statements at the commission on Wednesday, saying they showed "toxic collusion" between business interests and the state.
But Eusebius McKaiser, an associate at the Wits Centre for Ethics, said Mpofu's remarks "can't be taken as purely legalistic just because he's a lawyer".
"Sometimes even opening statements in the inquiry can be politically loaded and can take on undertones of politicking," he said.