The Parisian club has now claimed the season-opening trophy on 14 different times.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a comfortable triumph in the showdown featuring the French league champions and the French Cup holders after Ousmane Dembele opened the net in the opening stages.
Yet, Marseille struck twice late to take a surprise advantage. Initially, the English forward 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 fortune, Goncalo Ramos snatched 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 key figure, stopping crucial attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to seal a 4-1 penalty victory.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this competition for the 12th time in the last 13 years.
