Jean de Villiers will lead South Africa during their three-Test series against England, which begins on Saturday.
The 31-year-old centre, who has won 72 caps, said: "My heart was in my throat when the coach [Heyneke Meyer] told me.
"I realise there is massive responsibility with this position. The real, hard work starts now."
Meyer will review the position at the end of the series with two other potential captains, Schalk Burger and Juan Smith, currently injured.
"Jean's leadership qualities are well established," said Meyer.
"He has always impressed me with his leadership on and off the field.
"Jean commands respect from everyone in South African rugby and in the short space of time we've worked together, Jean has shown that he understands what we want to achieve on the field."