The Parisian club has now claimed the prestigious trophy on 14 different occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and secure a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a comfortable triumph in the match between the Ligue 1 winners and the Coupe de France holders after the French winger opened the scoring early on.
However, the southern French side struck two times in the closing moments to take a shock lead. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a vital equaliser in the dying moments to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, saving crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for PSG to complete a 4-1 penalty win.
The record champions PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the past thirteen years.
