Pirates put out a valiant effort to show signs of life against an on-form Chiefs but ultimately fell short in the penalty shootout, with Daniel Akpeyi proving the hero.
The Buccaneers took the game to Amakhosi as Fortune Makaringe scored on his Derby debut but Leonardo Castro equalised to force the match into extra-time.
Referee Jelly Chavani and his assistants Zakhele Siwela and Athenkosi Ndongeni made some big decisions in the match, which included an offside call on Samir Nurkovic's goal in the first half.
A red card to Mthokozise Dube early on in the second half looked to have taken some wind out of Bucs' sails as The Glamour Boys took control of proceedings from then onward.
The intensity lessened somewhat from both sides in extra-time but a handball inside the box allowed Daniel Cardoso to give his side the lead from the spot in the 94th minute.
Substitute Gabadinho Mhango then brought a spark of life to Pirates as he scored with hs first touch of the match to force the match into a sudden-death shootout.
Akpeyi pulled off two saves to deny Ben Motshwari and Abel Mabaso, as Chiefs walked away 4-2 victors to end their four-year wait for a victory over their arch rivals.