The Parisian club has now secured the season-opening trophy on fourteen separate times.
The Parisian giants needed a stoppage-time leveler followed by a perfect spot-kick decider to get past Marseille in Kuwait and secure a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a comfortable win in the match between the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele opened the scoring early on.
However, Marseille fired twice late to seize a surprise advantage. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a crucial leveler in the dying moments to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for PSG 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 completing a league and cup double, have now won this trophy for the twelfth time in the last 13 seasons.
