The Parisian club has now claimed the season-opening trophy on 14 different times.
The Parisian giants required a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The European champions seemed to be coasting towards a straightforward triumph in the showdown featuring the Ligue 1 winners and the French Cup winners after the French winger found the scoring in the opening stages.
Yet, Marseille struck two times in the closing moments to seize a shock lead. First, the English forward scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a vital leveler in the final moments to force the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, saving decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for PSG to seal a convincing penalty win.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this competition for the 12th time in the past 13 years.
