PSG has now claimed the season-opening trophy on 14 different occasions.
The Parisian giants needed a dramatic leveler followed by a successful spot-kick decider to overcome Marseille in Kuwait and secure a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a straightforward triumph in the showdown featuring the Ligue 1 winners and the French Cup holders after Ousmane Dembele opened the net in the opening stages.
However, the southern French side fired twice in the closing moments to seize a surprise advantage. First, Mason Greenwood converted from the spot-kick, before the defender inadvertently directed 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 moments to send the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, stopping crucial kicks from 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 4-1 shootout win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this trophy for the 12th time in the last 13 seasons.
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