PSG has now won the prestigious trophy on fourteen different times.
The Parisian giants required a stoppage-time leveler followed by a successful spot-kick decider to get past Marseille in the Gulf and capture a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting towards a comfortable win in the match featuring the French league winners and the French Cup winners after Ousmane Dembele found the net in the opening stages.
Yet, Marseille fired two times in the closing moments to take a shock advantage. First, Mason Greenwood converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos snatched a vital leveler in the dying moments to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored with composure for Paris Saint-Germain to seal a convincing penalty win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the past 13 years.
