PSG has now secured the prestigious trophy on 14 separate times.
Paris Saint-Germain required 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 victory.
The Champions League holders seemed to be coasting towards a comfortable triumph in the match between the French league winners and the Coupe de France winners after the French winger found the net early on.
Yet, the southern French side fired two times in the closing moments to take a surprise advantage. First, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a crucial leveler in the final seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored with composure for Paris Saint-Germain to seal a convincing shootout win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the past 13 years.
