The Parisian club has now secured the season-opening cup on fourteen different occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions title.
The European champions appeared to be sailing towards a comfortable triumph in the showdown featuring the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele opened the net early on.
Yet, Marseille fired two times late to seize a surprise lead. Initially, the English forward scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker snatched a vital leveler in the dying moments to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for PSG to seal a convincing penalty victory.
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 competition for the twelfth time in the past thirteen seasons.
