The Parisian club has now secured the prestigious cup on 14 separate occasions.
The Parisian giants needed 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 seemed to be coasting towards a comfortable win in the match featuring the Ligue 1 winners and the Coupe de France holders after the French winger found the scoring early on.
However, the southern French side fired twice in the closing moments to seize a surprise lead. First, Mason Greenwood scored from the penalty spot, 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 seconds to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to complete a convincing shootout win.
The record winners PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the last thirteen seasons.
