PSG has now won the prestigious cup on 14 separate times.
Paris Saint-Germain needed a dramatic equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a comfortable triumph in the showdown featuring the French league winners and the French Cup winners after Ousmane Dembele found the net in the opening stages.
However, the southern French side fired two times late to seize a surprise advantage. Initially, the English forward scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a vital leveler in the dying seconds to force the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, stopping crucial attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted with composure for PSG to complete a 4-1 penalty victory.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this trophy for the 12th time in the past 13 seasons.
