It ended 2-2 after 90 minutes, forcing the clash into extra time where neither side could carve out another clear-cut opening. Rise and Shine then went on to secure the win in the penalty shoot-out.
Rendani Ndou grabbed an early lead for the visitors in the second minute of the match following great work on the right wing by Rodney Ramagalela, who beat his marker inside the box and squared for Ndou to head into an empty net.
Defender Ntsikelelo Nyauza replied for the Buccaneers in the 12th minute with a striker's finish inside the box, after Rise and Shine failed to clear their lines.
Thamsanqa Gabuza squandered a golden chance to put the home side ahead in the 22nd minute when he blazed over the crossbar from six-yards out.
George Chigova conceded a penalty in the 27th minute after bringing Gabuza down in the area with a sliding tackle. Mpho Makola stepped up to take the penalty but saw his spot-kick saved by the Polokwane shot-stopper.
Chigova was injured from the tackle he made on Gabuza and had to be stretched off the field as he could not continue.
Milutin Sredojevic's charges were caught napping at the back as Ndou got his second goal of the match from inside the box three minutes before halftime after being put through by Jabulani Maluleke, 1-2.
However, Makola redeemed himself on the stroke of halftime by heading home a cross from Gabuza at the far post, 2-2.
Thabo Matlaba hit the post in added time but the score remained 2-2 at the halftime break.
Pirates took control of the contest in the second half, but chances were few and far between in the opening 15 minutes.
Mark van Heerden had an opportunity to put Pirates ahead in the 77th minute but his curling strike from just outside the box sailed over the crossbar.
Van Heerden had another chance with a screamer from outside the box five minutes before time but his powerful strike sailed narrowly wide.
The match eventually went into extra-time tied after it ended 2-2 after regulation time.
Bongile Booi should have sent Rise and Shine into the lead in the fourth minute of extra-time after being sent one-on-one with Wayne Sandilands but his strike sailed over the bar.
Thabo Qalinge was replaced by Riyaad Norodien in the 11th minute of extra time in a like-for-like change and a fresh pair of legs for the Buccaneers.
Makola was also withdrawn in the 20th minute and Thabo Rakhale came on in his place with the penalty shoot-out looming.
The score remained 2-2 after 120 minutes, forcing the clash into a penalty shoot-out, where Rise and Shine triumphed 4-2 to advance to the last four.