PSG has now won the season-opening trophy on 14 separate occasions.
Paris Saint-Germain needed a dramatic equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be sailing towards a straightforward win in the match featuring the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele opened the net early on.
Yet, Marseille fired twice late 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 remarkable turn of events, Goncalo Ramos grabbed a vital leveler in the dying seconds to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving decisive attempts from O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for PSG to seal a convincing shootout win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this competition for the 12th time in the past 13 seasons.