With Pirates not seeded after finishing outside, the teams found each other in different pots for the draw, with the positivity of meeting each other. However, Chiefs drew AmaZulu at home, while Pirates drew Golden Arrows away.
Meanwhile, defending champions Cape Town City will start their title defence with an away match to Baroka FC.
The Last 16 matches will be played on the weekend of October 28-29.
The full fixtures:
Baroka vs Cape Town City
Chippa United vs Mamelodi Sundowns
Bloemfontein Celtic vs SuperSport United
Polokwane City vs Ajax Cape Town
Kaizer Chiefs vs AmaZulu
Bidvest Wits vs Free State Stars
Maritzburg United vs Platinum Stars
Golden Arrows vs Orlando Pirates