PSG has now claimed the prestigious cup on 14 separate times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful penalty shootout to get past their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be sailing towards a comfortable triumph in the match between the French league champions and the Coupe de France holders after the French winger found the net early on.
Yet, Marseille struck two times late to take a shock advantage. 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 twist of events, the Portuguese striker snatched a vital equaliser in the final seconds to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to complete a 4-1 shootout win.
Now 14-time champions PSG, who met last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last 13 years.
