The Parisian club has now secured the prestigious cup on fourteen different times.
The Parisian giants needed a dramatic leveler followed by a successful penalty shootout to get past their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a comfortable triumph in the showdown featuring the Ligue 1 winners and the French Cup winners after Ousmane Dembele opened the scoring in the opening stages.
However, the southern French side struck twice in the closing moments to take a shock lead. First, the English forward converted from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a vital leveler in the final moments to send the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, saving crucial attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all converted with composure for Paris Saint-Germain to complete a convincing shootout victory.
The record winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this trophy for the twelfth time in the last 13 seasons.