The Parisian club has now won the prestigious trophy on 14 different times.
The Parisian giants needed a dramatic leveler followed by a perfect penalty shootout to get past Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be sailing towards a straightforward triumph in the match between the Ligue 1 champions and the French Cup winners after the French winger found the net early on.
Yet, Marseille struck two times in the closing moments to seize a surprise advantage. Initially, the English forward scored from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of events, the Portuguese striker grabbed a vital leveler in the final moments to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving decisive attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to complete a 4-1 shootout win.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the past 13 years.
