The Parisian club has now claimed the season-opening trophy on fourteen separate times.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be coasting towards a straightforward win in the showdown featuring the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele found the net in the opening stages.
However, the southern French side struck twice in the closing moments to take a shock lead. Initially, the English forward scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker grabbed a vital leveler in the dying seconds to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping crucial kicks from O'Riley and Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for PSG to complete a convincing penalty victory.
Now 14-time winners PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the past 13 years.