Madiba, who already has three children with Zuma, attended the president's inauguration in May, where she was treated as one of the country's three first ladies.
Multiple marriages form part of Zulu culture but are mostly practised in rural areas.
Zuma's embrace of Zulu tradition has endeared him to many South Africans but his polygamous lifestyle has been criticised by some, especially by women's rights activists.
The practise of polygamy has also drawn criticism from HIV/Aids activists in South Africa which has the highest infection rate in the world.
Zuma has 19 children, according to his official biography on the presidency website.
Even while preparations for Monday's wedding were under way, Zuma was reportedly preparing for his sixth marriage.
Earlier this week, a gift-giving ceremony was held signalling that he had paid dowry to the family of Bongi Ngema, his latest fiancee.
Zuma is already married to Sizakele Zuma, 67, his first wife whom he wed in 1973, and Nompumelelo Ntuli-Zuma who he married in 2007. Both women live in Nkandla.
He was previously married to Nkosazana Dlamini-Zuma, the country's home minister, whom he divorced in 1998 and Kate Mantsho-Zuma who committed suicide in 2000.
Zuma, whose tribe is South Africa's biggest, has repeatedly defended his decision to take many wives.
"There are plenty of politicians who have mistresses and children that they hide so as to pretend they are monogamous. I prefer to be open. I love my wives and I am proud of my children," Zuma once said in a television interview.