PSG has now claimed the prestigious trophy on 14 different times.
The Parisian giants required a dramatic equaliser followed by a perfect spot-kick decider to get past Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be sailing towards a straightforward triumph in the match between the French league winners and the French Cup holders after Ousmane Dembele found the scoring in the opening stages.
However, the southern French side struck two times late to take a surprise lead. 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 breathtaking turn of events, the Portuguese striker snatched a crucial equaliser in the dying seconds to send the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to complete a convincing shootout victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this trophy for the 12th time in the last 13 seasons.
