PSG has now claimed the season-opening cup on 14 separate times.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a fourth straight Trophee des Champions title.
The Champions League holders seemed to be sailing towards a comfortable win in the showdown featuring the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele found the net in the opening stages.
Yet, Marseille fired twice late to seize a shock lead. First, Mason Greenwood converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a crucial equaliser in the dying moments to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, stopping decisive kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to seal a 4-1 shootout win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the last 13 years.
