The Parisian club has now secured the season-opening cup on 14 different times.
Paris Saint-Germain needed a stoppage-time leveler followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and capture a fourth straight French Super Cup title.
The European champions appeared to be sailing towards a straightforward win in the match between the French league champions and the Coupe de France winners after Ousmane Dembele found the scoring in the opening stages.
Yet, Marseille struck two times late to take a surprise advantage. Initially, the English forward scored from the penalty spot, before the defender unfortunately turned 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 dying moments to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for PSG to complete a convincing shootout victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the past 13 seasons.
