The Parisian club has now won the prestigious cup on 14 different times.
The Parisian giants required a stoppage-time leveler followed by a successful penalty shootout to get past their arch-rivals in Kuwait and capture a fourth straight French Super Cup victory.
The European champions seemed to be coasting towards a straightforward triumph in the match between the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele opened the net early on.
However, Marseille struck two times late to take a shock advantage. First, the English forward converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of events, the Portuguese striker snatched a crucial equaliser in the final seconds to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving crucial kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for PSG to complete a 4-1 shootout win.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the past 13 years.
