PSG has now claimed the prestigious cup on fourteen different occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect spot-kick decider 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 showdown between the French league champions and the French Cup winners after Ousmane Dembele opened the scoring in the opening stages.
Yet, the southern French side struck two times late to take a surprise lead. Initially, the English forward converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos snatched a vital leveler in the final moments to force the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for PSG to complete a 4-1 penalty win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the past thirteen years.
