The Parisian club has now won the season-opening trophy on fourteen different occasions.
Paris Saint-Germain required a dramatic equaliser followed by a successful penalty shootout to get past Marseille in Kuwait and capture a fourth straight French Super Cup title.
The Champions League holders seemed to be sailing towards a straightforward triumph in the match between the French league champions and the Coupe de France winners after the French winger opened the scoring early on.
However, Marseille struck twice late to seize a surprise lead. First, 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 breathtaking turn of fortune, the Portuguese striker snatched a vital leveler in the dying moments to send the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for PSG to complete a 4-1 penalty victory.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the last 13 seasons.
