PSG has now claimed the prestigious cup on 14 separate occasions.
The Parisian giants needed a stoppage-time equaliser followed by a perfect penalty shootout to get past Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be coasting towards a straightforward win in the match featuring the French league winners and the French Cup winners after Ousmane Dembele opened the net early on.
Yet, the southern French side struck two times in the closing moments to take a surprise advantage. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a vital equaliser in the dying seconds to send the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping decisive kicks from Matt O'Riley and Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to seal a convincing penalty win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this trophy for the twelfth time in the last thirteen seasons.
