Fadlu Davids' men dominated first half proceedings and having made a very bright start to the game, they had early chances as Yannick Zakri's sixth minute free kick was saved before Siphesihle Ndlovu shot wide on 13 minutes after Fortune Makaringe and Mohau Mokate had combined well.
There was another opportunity for United in the 17th minute when Mokate's shot from the edge of the box was saved by home keeper Harold Ndlovu, before his namesake Ndlovu blasted over the bar from the rebound for the KZN team.
There was also an opening for Justice Figareido, whose half-volley was off-target.
Team of Choice goalkeeper Richard Ofori was meanwhile only called into action on 31 minutes when he pouched a 20-yard shot fired in from Walter Musona.
After a quiet start to the second half which saw neither team able to create chances on goal, Rise and Shine took the lead on the hour mark when Jabulani Maluleka teed Edgar Manaka, who scored with a well-taken curling effort into the top corner.
Maritzburg came backing fighting as they looked for an equaliser, but apart from a squandered chance from Bandile Shandu 15 minutes from time, they battled to penetrate a determined Polokwane City defence and were forced to make the trip home without anything to show for their efforts.
Next up for United is their Telkom Knockout last eight clash with Bidvest Wits at the Harry Gwala Stadium on Saturday 3 November.
Polokwane: Ndlovu, Nkili, Mngomezulu, Hlongwane, Motloung , Seabi, Manaka, Maluleke, Phiri, Ramagalela, Musona.
Subs: Baloyi, Booi Sikhondze, Mbonani, Wagaba, Mvelase, Phali.
Maritzburg: Ofori, Sanoka, Xulu, Shandu, Figariedo, De Reuck, Allie, Makaringe, Zakri, Ndlovu, Mokate.
Subs: Mpandle, Kunene, Fileccia, Matima, Mekoa, Makgalwa, Thlone.
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