The Parisian club has now secured the season-opening cup on fourteen different occasions.
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 title.
The European champions seemed to be coasting towards a comfortable triumph in the showdown between the French league champions and the Coupe de France holders after the French winger opened the scoring in the opening stages.
However, the southern French side fired twice in the closing moments to seize a surprise advantage. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of events, Goncalo Ramos snatched a crucial leveler in the final seconds to send the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for PSG to complete a convincing shootout victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this competition for the twelfth time in the last thirteen years.