PSG has now won the season-opening trophy on fourteen 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 French Super Cup victory.
The Champions League holders seemed to be coasting towards a straightforward win in the showdown between the French league champions and the Coupe de France winners after Ousmane Dembele found the scoring in the opening stages.
Yet, the southern French side fired twice in the closing moments to seize a shock advantage. First, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos snatched a vital equaliser in the final seconds to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, saving decisive kicks from O'Riley and Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to seal a convincing penalty win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this trophy for the twelfth time in the past thirteen seasons.
