PSG has now claimed the prestigious cup on 14 different occasions.
The Parisian giants needed 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 European champions seemed to be sailing towards a straightforward triumph in the match featuring the French league winners and the Coupe de France holders after Ousmane Dembele found the net in the opening stages.
However, Marseille fired two times late to seize a shock advantage. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a vital leveler in the dying seconds to send the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for PSG to seal a 4-1 penalty win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the past 13 seasons.
