PSG has now won the season-opening trophy on 14 separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting towards a straightforward triumph in the showdown between the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the net early on.
However, the southern French side struck two times in the closing moments to take a surprise advantage. Initially, Mason Greenwood converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of events, the Portuguese striker grabbed a crucial equaliser in the dying seconds to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping decisive attempts from Matt O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for PSG to seal a convincing penalty win.
The record winners PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this trophy for the 12th time in the last 13 seasons.
