The Parisian club has now won the prestigious trophy on 14 different times.
The Parisian giants required a stoppage-time leveler followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The Champions League holders appeared to be sailing towards a straightforward win in the showdown featuring the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the scoring early on.
Yet, the southern French side struck twice in the closing moments to take a shock lead. First, the English forward scored from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a crucial equaliser in the final seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, saving decisive attempts from Matt O'Riley and Traore.
In the shootout, Ramos, the midfielder, the full-back, and the young talent all converted successfully for PSG to seal a 4-1 shootout win.
The record winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this trophy for the 12th time in the past thirteen years.
