PSG has now won the season-opening cup on fourteen different occasions.
The Parisian giants needed a stoppage-time equaliser followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions title.
The Champions League holders appeared to be coasting towards a comfortable triumph in the match between the French league winners and the French Cup holders after Ousmane Dembele opened the scoring in the opening stages.
However, Marseille fired twice in the closing moments to seize a shock advantage. Initially, the English forward scored from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker snatched a vital equaliser in the dying moments to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for PSG to seal a convincing shootout victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this competition for the twelfth time in the past 13 years.