The Parisian club has now won the prestigious cup on 14 different times.
The Parisian giants needed a dramatic equaliser followed by a successful penalty shootout to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The European champions seemed to be coasting towards a straightforward triumph in the showdown between the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele opened the scoring early on.
However, the southern French side struck two times in the closing moments to seize a surprise lead. First, Mason Greenwood scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker snatched a vital equaliser in the final seconds to force the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, stopping decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all converted successfully for PSG to seal a convincing shootout win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the past thirteen years.