The match ended 1-1 and the 4-2 aggregate score means that Pirates embarrassingly bowed out of the African Champions League in the first round.
De Libolo had put themselves in the driver's seat when they beat the Buccaneers in the first leg in Port Elizabeth two weeks ago.
Bucs' early departure will infuriate boss Irvin Khoza, who had invested heavily for this African safari. Pirates' main aim this season was to emulate the Class of 1995 by lifting the trophy.
Pirates struggled to settle down yesterday with Recreativo De Libolo out-muscling them and defending solidly. Pirates resorted to speculative long-range efforts that did not threaten the Angolans.
The home side almost ended all hope the South Africans harboured when they opened the scoring in the 32nd minute through a Maieco Herique header from a corner.
But Pirates did not drop their heads and Andile Jali's equaliser on half time gave them a glimmer of hope.
They had the Angolans on the ropes for the entire second half but goals eluded them.
Tlou Segolela and substitute Benni McCarthy came close to scoring but it was not to be as Khoza's dream of conquering Africa went up in smoke.