PSG has now claimed the season-opening trophy on 14 different occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders seemed to be sailing towards a straightforward triumph in the match featuring the Ligue 1 winners and the French Cup winners after Ousmane Dembele found the net in the opening stages.
Yet, Marseille struck twice in the closing moments to take a shock lead. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of events, the Portuguese striker snatched a crucial leveler in the final seconds to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to seal a 4-1 shootout win.
Now 14-time winners PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this trophy for the 12th time in the last thirteen years.
