The Parisian club has now claimed the season-opening cup on fourteen separate occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup victory.
The European champions seemed to be sailing towards a comfortable win in the showdown featuring the French league winners and the Coupe de France holders after the French winger opened the scoring in the opening stages.
However, the southern French side struck two times in the closing moments to take a shock lead. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker grabbed a vital leveler in the final seconds to send the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all converted with composure for Paris Saint-Germain to complete a 4-1 shootout win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the last 13 seasons.
