The Parisian club has now claimed the season-opening trophy on 14 different occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect penalty shootout to overcome Marseille in Kuwait and secure a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a comfortable win in the showdown between the French league champions and the Coupe de France winners after the French winger found the scoring early on.
However, the southern French side fired twice in the closing moments to seize a surprise lead. First, the English forward 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 events, Goncalo Ramos snatched a vital leveler in the final seconds to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to complete a 4-1 shootout victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this trophy for the 12th time in the past 13 seasons.
