PSG has now secured the season-opening cup on fourteen separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a successful penalty shootout 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 sailing towards a straightforward triumph in the showdown between the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele found the scoring in the opening stages.
Yet, the southern French side fired two times late to take a surprise lead. Initially, the English forward converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a crucial leveler in the final seconds to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to seal a 4-1 shootout win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now lifted this competition for the 12th time in the past 13 seasons.