PSG has now secured the prestigious trophy on fourteen separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be sailing towards a comfortable win in the showdown between the French league winners and the French Cup holders after the French winger found the net early on.
However, Marseille fired two times late to seize a shock lead. Initially, Mason Greenwood scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a crucial leveler in the final seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to seal a 4-1 penalty win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this trophy for the 12th time in the last thirteen years.
