This came after unconfirmed reports that Ramaphosa had expressed the wish to attend events marking the anniversary of the killing of dozens of striking miners for the first time in five years.
On August 16, 2012, police gunned down 34 mineworkers who were participating in a protracted strike at platinum miner, Lonmin, after wage negotiations broke down. They were demanding that their salaries be increased to R12 500.
Mathunjwa last month said that if Ramaphosa wanted to come to Marikana, he must arrange another date to meet with the widows of the slain miners.
"We had a meeting with Marikana widows. They said that Deputy President Cyril Ramaphosa is not welcome in Marikana. Marikana widows have made it quite clear that he is not welcome there for now. They need space," Mathunjwa said.
"I don't think it is out of genuine and sincere heart. He believes Marikana would be a good place for him to campaign."
Ramaphosa has thrown his hat in the ring to become the next president of the African National Congress when the ruling party holds its elective conference in December.
In May this year, Ramaphosa apologised for a series of nine emails which he wrote to other Lonmin executives and government ministers in the days leading to the massacre, saying he was sorry for the type of language he used at the time.
He was non-executive director at Lonmin's platinum mines at the time.
On the eve of the Marikana shooting, Ramaphosa said in an email discussion between Lonmin management and government officials that events around the strike - of Amcu-affiliated miners - "are plainly dastardly criminal acts and must be characterised as such". He also called for "concomitant action" to be taken.
Ramaphosa's presidential bid has been endorsed by Amcu's rival in the mining sector, the ANC-aligned National Union of Mineworkers (NUM). Ramaphosa was NUM's first general secretary when the union was launched in 1982.