The Parisian club has now secured the prestigious cup on 14 different times.
Paris Saint-Germain needed a stoppage-time leveler followed by a perfect spot-kick decider to get past Marseille in Kuwait and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a comfortable win in the match featuring the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele opened the net in the opening stages.
However, the southern French side struck twice in the closing moments to seize a surprise lead. First, Mason Greenwood scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a crucial equaliser in the dying moments to force the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping decisive attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to seal a convincing penalty victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the past 13 years.
