Stuart Baxter saw his team twice taking the lead, only to allow Rise and Shine back in to the game each time, before Thuso Phala grabbed a 77th minute winner.
SuperSport were off to the perfect start when Morgan Gould powered home a header from Tebogo Mokoena’s perfectly placed cross before a minute was even on the clock.
The Tshwane team remained on top and were close to scoring a second five minutes later, but Rise and Shine keeper George Chigova did well to tip Jeremy Brockie’s shot around the post.
Polokwane began to get themselves back into the game and they levelled matters just before the half hour mark when Tshepo Tema sent in a thumping header at the far post following Simphiwe Hlongwane’s inviting cross.
The home side then went close to taking the lead two minutes before the break when Rodney Ramagalela beat the off-side trap, but SuperSport keeper Ronwen Williams did well to intervene, before Vusimuzi Mngomezulu fired wide on the follow-up.
After a tense opening to the second half, SuperSport were to reclaim the lead in the 57th minute via a sensational volley from Brockie, the New Zealand international curling a left-footed volley into the top corner from a very tight angle.
Again though the visitors from Pretoria were to allow Polokwane City back into the game when Mngomezulu beat Williams from a tight angle on the right after Dean Furman had lost the ball to Jabu Maluleke.
However, Matsatsantsa took the lead for the third and last occasion, 13 minutes before the end, when Reneilwe Letsholonyane slipped a sublime pass for Phala, who finished clinically into the bottom corer of the net.
Williams made an acrobatic save to stop Edgar Manaka from heading in an equaliser while at the other end Brockie struck the woodwork before the full time whistle finally blew on a highly entertaining game in the Limpopo Province.