The band will top the bill at the My Coke Fest, which takes place over two days in Johannesburg and Cape Town.
Other acts due to play include Kaiser Chiefs, Korn, Chris Cornell, Good Charlotte and South African rockers Prime Circle.
It is the third year the festival has taken place and it has been headlined by Metallica, Hoobastank and Staind in the past.
Guns 'n' Roses were due to play last year's event but pulled out at the last moment.
The two-day festival starts on March 21 at Johannesburg's New Market Racecourse and ends on March 24 at Kenilworth Racecourse in Cape Town.