The Parisian club has now won the season-opening trophy on 14 separate times.
The Parisian giants required a stoppage-time equaliser followed by a perfect penalty shootout to overcome their arch-rivals in Kuwait and secure a fourth straight French Super Cup title.
The European champions seemed to be coasting towards a comfortable triumph in the showdown between the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele opened the net early on.
However, Marseille fired two times in the closing moments to take a surprise lead. First, Mason Greenwood scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of events, the Portuguese striker grabbed a vital leveler in the dying moments to send the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored successfully for PSG to seal a 4-1 penalty victory.
Now 14-time winners Paris Saint-Germain, who faced 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 seasons.
