The Parisian club has now won the season-opening cup on fourteen separate occasions.
The Parisian giants needed a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a comfortable win in the showdown featuring the French league champions and the Coupe de France winners after the French winger opened the net early on.
However, the southern French side fired two times late to take a surprise advantage. Initially, the English forward scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a crucial equaliser in the final seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for PSG to seal a convincing penalty win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this trophy for the 12th time in the last 13 years.
