The Parisian club has now won the prestigious trophy on fourteen separate times.
The Parisian giants required a stoppage-time leveler followed by a perfect spot-kick decider to overcome Marseille in Kuwait and secure a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a comfortable triumph in the showdown between the French league winners and the French Cup holders after Ousmane Dembele opened the scoring in the opening stages.
However, the southern French side struck twice in the closing moments to seize a shock advantage. First, Mason Greenwood converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos snatched a crucial equaliser in the dying moments to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, saving crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for PSG to complete a convincing shootout victory.
The record winners PSG, who faced last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the last 13 seasons.
