The Parisian club has now won the season-opening cup on 14 different times.
The Parisian giants needed a stoppage-time equaliser followed by a perfect penalty shootout to overcome Marseille in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be sailing towards a comfortable triumph in the showdown between the Ligue 1 champions and the Coupe de France winners after the French winger opened the scoring early on.
Yet, the southern French side fired twice late to seize a shock lead. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a vital equaliser in the final moments to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored with composure for PSG to complete a convincing shootout victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the past thirteen years.
