PSG has now claimed the season-opening cup on 14 separate occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect 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 appeared to be coasting towards a comfortable win in the showdown between the Ligue 1 winners and the French Cup winners after the French winger found the scoring early on.
However, the southern French side fired twice in the closing moments to seize a surprise lead. First, Mason Greenwood converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a remarkable turn of events, the Portuguese striker grabbed a vital equaliser in the dying moments to send the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to seal a convincing shootout win.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last thirteen seasons.
