PSG has now secured the season-opening cup on fourteen separate times.
Paris Saint-Germain needed a stoppage-time leveler followed by a perfect spot-kick decider to get past Marseille in Kuwait and secure a fourth straight French Super Cup title.
The Champions League holders appeared to be sailing towards a comfortable win in the showdown featuring the Ligue 1 winners and the French Cup holders after Ousmane Dembele opened the scoring in the opening stages.
Yet, Marseille fired two times in the closing moments to seize a shock lead. Initially, Mason Greenwood scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a vital equaliser in the final seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for PSG to complete a convincing penalty victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the last 13 seasons.
