PSG has now won the prestigious cup on fourteen separate occasions.
The Parisian giants required a stoppage-time equaliser followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and capture a fourth straight French Super Cup title.
The Champions League holders seemed to be sailing towards a comfortable win in the match between the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele opened the scoring early on.
However, Marseille struck two times late to take a surprise lead. First, the English forward scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, Goncalo Ramos snatched a vital equaliser in the dying seconds to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving crucial attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for Paris Saint-Germain to complete a convincing penalty win.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this competition for the 12th time in the last 13 years.
