PSG has now secured the season-opening trophy on fourteen different times.
Paris Saint-Germain required a dramatic equaliser followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The Champions League holders appeared to be coasting towards a comfortable triumph in the match between the Ligue 1 winners and the French Cup holders after the French winger found the scoring in the opening stages.
Yet, the southern French side struck twice in the closing moments to take a surprise lead. First, the English forward converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a vital leveler in the final seconds to send the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for PSG to seal a convincing shootout win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this trophy for the 12th time in the last thirteen seasons.
