Pirates have been given a tricky encounter as they hosts Bidvest Wits, who already defeated the Soweto giants in the Absa Premiership this season.
Defending champions TS Galaxy, who famously defeated Kaizer Chiefs in the final, will began their defence against last season's semi-finalists Chippa United.
There will be two derbies in the round of 32 as Mamelodi Sundowns take on SuperSport United, while Polokwane City host Baroka FC.
The Premier Soccer League league will announce the dates and venues in due course.
Polokwane City vs Baroka FC
Zizwe United vs Happy Wanderers
Stellenbosch vs Maritzburg United
Orlando Pirates vs Bidvest Wits
Amavarara vs Super Eagles
Vaal University of Technology vs Golden Arrows
Chippa United vs TS Galaxy
Bloemfontein Celtic vs AmaZulu
Mbombela United vs Cape Town City
Black Leopards vs North West University
Mamelodi Sundowns vs SuperSport United
Kaizer Chiefs vs Royal Eagles
Highlands Park vs Uthongathi FC
Passion FC vs Real Kings
Ajax Cape Town vs TS Sporting
Jomo Cosmos vs Hungry Lions