The Parisian club has now claimed the season-opening cup on 14 different times.
Paris Saint-Germain needed a dramatic equaliser followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a comfortable triumph in the match between the French league champions and the Coupe de France winners after Ousmane Dembele found the net in the opening stages.
However, Marseille fired twice in the closing moments to seize a shock advantage. Initially, the English forward scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker grabbed a crucial leveler in the final seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving crucial attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for PSG to seal a 4-1 penalty victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this competition for the twelfth time in the last thirteen years.
