PSG has now won the season-opening trophy on 14 separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect penalty shootout to get past Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be coasting towards a comfortable win in the match between the Ligue 1 winners and the Coupe de France holders after the French winger opened the net early on.
Yet, Marseille struck twice late to seize a shock lead. Initially, 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, Goncalo Ramos snatched a vital equaliser in the dying moments to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping crucial attempts from Matt O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for PSG to complete a 4-1 penalty win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this trophy for the twelfth time in the past thirteen seasons.
