PSG has now claimed the prestigious cup on 14 different times.
The Parisian giants required a dramatic equaliser followed by a successful penalty shootout to overcome their arch-rivals in Kuwait and capture a fourth straight French Super Cup title.
The Champions League holders appeared to be sailing towards a straightforward win in the match between the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele found the scoring early on.
However, Marseille struck twice in the closing moments to take a shock advantage. First, the English forward converted from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos snatched a vital leveler in the dying seconds to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, stopping crucial kicks from O'Riley and Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to seal a 4-1 shootout win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this competition for the 12th time in the last 13 years.
