The Parisian club has now won the prestigious cup on 14 separate times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect penalty shootout to get past their arch-rivals in Kuwait and secure a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a comfortable triumph in the match between the French league champions and the French Cup holders after the French winger found the scoring in the opening stages.
Yet, Marseille fired twice in the closing moments to seize a surprise advantage. First, Mason Greenwood converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable turn of fortune, the Portuguese striker snatched a crucial equaliser in the final seconds to force the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping crucial attempts from O'Riley and Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to complete a convincing penalty victory.
The record champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this competition for the 12th time in the last thirteen seasons.
