PSG has now claimed the season-opening trophy on 14 separate occasions.
Paris Saint-Germain required a dramatic equaliser followed by a perfect penalty shootout to overcome Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be sailing towards a comfortable triumph in the match between the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele found the net in the opening stages.
Yet, Marseille struck twice in the closing moments to seize a shock advantage. First, the English forward scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a crucial leveler in the final seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for PSG to seal a convincing penalty win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this competition for the 12th time in the past 13 years.
