PSG has now won the prestigious cup on fourteen different occasions.
The Parisian giants required a dramatic equaliser followed by a successful 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 win in the match featuring the Ligue 1 winners and the Coupe de France winners after the French winger found the scoring early on.
However, the southern French side fired two times in the closing moments to seize a surprise lead. First, Mason Greenwood converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of events, the Portuguese striker grabbed a vital equaliser in the final seconds to send the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, saving crucial attempts from O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for PSG to seal a convincing penalty victory.
The record champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this trophy for the 12th time in the last 13 years.
