Mr Ramaphosa, a close confidante of the late Nelson Mandela, was deputy under President Jacob Zuma.
He was the only candidate nominated by parliament, which is dominated by his African National Congress. MPs broke into song at the announcement.
In his first presidential speech, Mr Ramaphosa, 65, said he would tackle the corruption which allegedly became widespread under Mr Zuma.
His predecessor Mr Zuma’s two terms as president had been dogged by corruption allegations, his relationship with the powerful Gupta family and several issues.
The ANC had told Mr Zuma to step down or face a vote of no-confidence.
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Mr Zuma faces numerous corruption allegations but denies any wrongdoing.
Will his emergence bring back the Reputation of ANC?