PSG has now won the prestigious trophy on fourteen separate occasions.
The Parisian giants required a dramatic equaliser followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a straightforward win in the match between the French league champions and the French Cup winners after Ousmane Dembele found the net in the opening stages.
However, Marseille fired two times in the closing moments to take a shock advantage. First, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a vital leveler in the final seconds to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to seal a convincing penalty win.
The record champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this competition for the 12th time in the past thirteen seasons.
