PSG has now secured the prestigious trophy on 14 separate times.
The Parisian giants needed a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be sailing towards a straightforward win in the match featuring the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele opened the net early on.
However, Marseille fired twice late to take a surprise advantage. Initially, the English forward scored from the spot-kick, before the defender unfortunately turned the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos snatched a crucial leveler in the final moments to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, stopping decisive kicks from O'Riley and Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to seal a convincing penalty victory.
The record winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this trophy for the 12th time in the last thirteen seasons.
