Democratic Alliance (DA) leader Helen Zille made her mark at St Paul's Anglican Church in Rondebosch in Cape Town just after 9 a.m., accompanied by her husband Johann Maree.
Zille is the premier of the Western Cape and the DA has been pushing to retain the province and increase its support in the national and provincial ballot in these elections.
Agang SA leader Mamphela Ramphele surprised voters when she arrived to make her mark at the Sea Point library voting station in Cape Town.
Julius Malema, the leader of the new kid on the block, Economic Freedom Fighters, arrived two hours after the voting station opened in his hometown, to vote at Mponegele Primary School in Seshego, while Congress of the People leader Mosiuoa Lekota voted in his hometown of Bloemfontein in the Free State.