The Parisian club has now secured the season-opening trophy on 14 separate times.
The Parisian giants required a dramatic leveler followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be coasting towards a comfortable triumph in the match featuring the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the net in the opening stages.
Yet, the southern French side struck two times late to seize a surprise lead. First, the English forward scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a vital leveler in the final seconds to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored with composure for Paris Saint-Germain to seal a convincing penalty win.
The record champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now lifted this competition for the 12th time in the past 13 years.
