PSG has now won the prestigious trophy on 14 different occasions.
Paris Saint-Germain needed a dramatic leveler followed by a successful penalty shootout to get past Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be sailing towards a straightforward win in the match between the French league winners and the French Cup holders after Ousmane Dembele found the net early on.
Yet, Marseille struck two times late to take a surprise advantage. First, the English forward scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker snatched a crucial leveler in the final moments to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping decisive attempts from Matt O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to complete a 4-1 shootout win.
The record champions PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this competition for the 12th time in the past 13 years.