On his second start for Orlando Pirates, defender Mbekezeli Mbokazi struck with his left foot off an attempt by SuperSport United to clear danger to break the deadlock on 29 minutes and his first ever professional goal.
But Matsatsantsa levelled two minutes before half-time through Terrence Dzvukamanja, who hit against his former paymasters.
In the stoppage time of the first half, Evidence Makgopa justified why he was started when he reclaimed the lead for the Buccaneers.
SuperSport came back again, this time in stoppage time, through the individual brilliance of Gape Moralo, who weaved his way past Pirates defenders before beating goalkeeper Sipho Chaine.
On an afternoon coach Gavin Hunt was suspended and not on the SuperSport bench, the match ended 2-2 after extra time, leading to penalty shootouts which ended 5-4 in favour of the Buccaneers.
Defending champions Pirates are now in the semi-finals of this competition.