The Parisian club has now secured the season-opening cup on fourteen different times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful penalty shootout to get past Marseille in Kuwait and capture a fourth straight French Super Cup victory.
The European champions seemed to be coasting towards a straightforward triumph in the showdown featuring the Ligue 1 winners and the French Cup winners after Ousmane Dembele found the net early on.
However, the southern French side struck twice late to seize a shock advantage. Initially, the English forward converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own goal.
In a remarkable twist of events, Goncalo Ramos snatched a vital leveler in the dying moments to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for PSG to seal a 4-1 shootout victory.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the last thirteen years.
