Chiefs, who are the most decorated team in the history of the tournament, will host National First Division (NFD) side Stellenbosch FC.
The two teams met during last year's competition with 13-time champions Chiefs securing a 3-0 win over Stellenbosch in the Mother City.
Amakhosi defeated Lamontville Golden Arrows in the Last 32, while Stellenbosch knocked out fellow NFD side Highlands Park.
The 2015 winners Sundowns will face off with ABC Motsepe side EC Bees, who lost to Pirates in last year's tournament.
Sundowns edged out NFD outfit Cape Town All Stars in the Last 32, while Bees beat Mariveni United away.
The tie of the round will feature Premier Soccer League (PSL) sides Pirates and Cape Town City.
Bucs, who are the second most successful team with eight trophies, will play host to the Citizens.
The Buccaneers booked their place in the Last 16 after brushing aside Ajax Cape Town at home, while City overcame the defending PSL champions Bidvest Wits.
Bloemfontein Celtic, who eliminated the defending champions SuperSport United, will face Richard Bay FC.
SuperSport won the last two tournaments, but they were stunned by Celtic in this year's Last 32.
Phunya Sele Sele are set to host Richards Bay, who are campaigning in the NFD.
Kaizer Chiefs v Stellenbosch
Cape Town City v Orlando Pirates
Royal Eagles v Maritzburg United
AmaZulu v Ubuntu Cape Town
Free State Stars v Chippa United
Mamelodi Sundowns v EC Bees FC
Bloemfontein Celtic v Richards Bay
Baroka v Steenberg United