The Parisian club has now won the season-opening trophy on fourteen separate times.
The Parisian giants needed a dramatic equaliser followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders appeared to be sailing towards a straightforward triumph in the match between the French league winners and the Coupe de France winners after Ousmane Dembele found the net early on.
However, the southern French side struck twice in the closing moments to take a shock advantage. Initially, Mason Greenwood scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker snatched a vital leveler in the final seconds to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving crucial attempts from O'Riley and Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for PSG to seal a 4-1 shootout victory.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this trophy for the 12th time in the last 13 seasons.
