There were three changes to United's side with Miguel Timm, Bandile Shandu and Thabiso Kutumela while City’s solitary change was bringing in Wiseman Maluleke.
Maritzburg were ahead within five minutes as their first attack led to Thabiso Kutumela nodding home Siphesihle Ndlovu’s rebound.
Polokwane's first chance on goal arrived in the form of a set-piece from the right side of the area, but Bongile Booi ultimately sent his header wide of the mark.
With 30 minutes played, the home side upped the momentum and doubled their lead through Mokate, who was well positioned to turn home Fortune Makaringe’s low cross from the right.
In response, Jozef Vukusic threw caution to the wind ten minutes before half-time through the arrival of Zimbabwean striker Charlton Mashumba.
Set up for an enterprising second half, Polokwane sunk deeper as Kutumela completed his brace through a well-worked move from the middle to make it 3-0 for the home side.
The visitors responded inside a few minutes as Mashumba’s header crashed off the underside of the bar into the net on 60 minutes after Richard Ofori failed to deal with a cross into the box.
The Team of Choice surprisingly removed their two-goal hero, Kutumela, for Mpho Matsi, signalling their intention to close out proceedings.
In contrast, the tempo from the home side failed to die down as Makaringe’s quest to enhance their tally was halted by the side-netting in the final 10 minutes.
Ofori ensured Polokwane did not get another goal as he produced a fine save in time added on. Maritzburg now sit two points adrift of safety after their first home win of the campaign.
Maritzburg: Ofori, Kunene, Xulu, De Reuck, Onyango, Makaringe, Timm, Kutumela, Ndlovu, Mokate, Shandu.
Subs: Mpandle, Allie, Matsi. Zakri. Figareido, Moseamedi, Mekoa.
Polokwane: Chigova, Mbonani, Nkili, Phiri, Kalake, Hlongwane, J.Maluleke, W.Maluleke, Seabi, Anas, Booi.
Subs: Phali, Wagaba, Mphambaniso, Sikhosana, Musona, Baloyi, Mashumba.