PSG has now secured the season-opening cup on 14 separate times.
The Parisian giants needed a dramatic leveler followed by a perfect penalty shootout to get past their arch-rivals in Kuwait and secure a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be coasting towards a comfortable win in the match between the French league champions and the French Cup winners after Ousmane Dembele found the net early on.
However, Marseille struck two times late to seize a shock advantage. Initially, Mason Greenwood converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker snatched a crucial leveler in the final seconds to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to complete a convincing shootout victory.
Now 14-time champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the last 13 seasons.
