Stars earned the match-up by qualifying from SAFA's Mpumalanga structures.
The Western's Cape's Steenberg United have also advanced to the next stage of the competition by defeating Magic FC in the play-offs. They will face cup rookies Orbit College.
The last-32 round consists of all 16 clubs from the Absa Premiership, eight sides from the NFD and eight from SAFA structures.
SuperSport United are bidding for a third straight Nedbank Cup triumph.
Mariveni United VS EC Bees
Swallows FC v Maritzburg United
Kaizer Chiefs v Golden Arrows
Cape Town All Stars v Mamelodi Sundowns
Phiva Young Stars v Chippa United
Orlando Pirates v Ajax Cape Town
Bidvest Wits v Cape Town City
AmaZulu v Mthatha Bucks
Super Eagles v Free State Stars
Platinum Stars v Baroka FC
Richards Bay v Bloemfontein Young Tigers
Stellenbosch FC v Highlands Park
Bloemfontein Celtic v SuperSport United
Happy Wanderers v Royal Eagles
Ubuntu Cape Town v Polokwane City
Steenberg United v Orbit College