The Parisian club has now claimed the prestigious trophy on 14 separate times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be sailing towards a straightforward triumph in the showdown featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele opened the net in the opening stages.
However, the southern French side fired twice late to take a shock lead. Initially, the English forward converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a remarkable turn of events, Goncalo Ramos snatched a crucial leveler in the final moments to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to seal a convincing penalty win.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the past 13 years.
