The Parisian club has now won the prestigious cup on fourteen separate occasions.
Paris Saint-Germain required a dramatic equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be coasting towards a straightforward triumph in the match between the French league champions and the Coupe de France holders after the French winger opened the scoring early on.
However, Marseille fired twice late to seize a shock advantage. First, Mason Greenwood scored from the spot-kick, before the defender unfortunately turned the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker snatched a vital leveler in the final seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to complete a convincing penalty win.
The record champions PSG, who met last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the past 13 seasons.
