The Parisian club has now claimed the season-opening cup on 14 separate times.
The Parisian giants needed a stoppage-time leveler followed by a successful penalty shootout to get past their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a straightforward win in the match featuring the Ligue 1 winners and the Coupe de France winners after the French winger found the scoring in the opening stages.
However, Marseille fired twice late to take a shock advantage. First, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a vital leveler in the final seconds to force the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to seal a 4-1 penalty victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the last thirteen years.
