PSG has now secured the prestigious cup on fourteen different occasions.
The Parisian giants needed a dramatic equaliser followed by a successful penalty shootout to get past Marseille in the Gulf and capture a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a comfortable triumph in the match featuring the French league champions and the Coupe de France holders after the French winger opened the scoring in the opening stages.
Yet, the southern French side fired twice late to seize a shock lead. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of events, Goncalo Ramos snatched a crucial leveler in the final moments to force the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, saving crucial attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for PSG to seal a 4-1 penalty win.
The record champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the past thirteen years.