PSG has now won the season-opening cup on 14 separate times.
The Parisian giants needed a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight Trophee des Champions victory.
The Champions League holders seemed to be sailing towards a comfortable win in the showdown between the French league winners and the Coupe de France winners after Ousmane Dembele opened the net in the opening stages.
Yet, Marseille struck twice late to seize a surprise lead. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a remarkable turn of events, Goncalo Ramos snatched a crucial equaliser in the dying seconds to send the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to seal a 4-1 penalty victory.
The record winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the last thirteen seasons.
