PSG has now won the prestigious trophy on fourteen different occasions.
Paris Saint-Germain required a dramatic equaliser followed by a perfect spot-kick decider to overcome Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be coasting towards a straightforward triumph in the showdown between the French league winners and the Coupe de France winners after Ousmane Dembele found the net in the opening stages.
Yet, Marseille fired two times late to seize a shock lead. First, the English forward converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a vital equaliser in the dying moments to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and the young talent all scored with composure for PSG to seal a 4-1 penalty victory.
The record champions 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 last 13 seasons.