PSG has now won the prestigious trophy on 14 separate occasions.
Paris Saint-Germain required a dramatic equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a straightforward triumph in the match featuring the French league winners and the French Cup winners after Ousmane Dembele opened the scoring in the opening stages.
Yet, Marseille fired two times late to take a shock lead. Initially, Mason Greenwood scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos snatched a crucial leveler in the dying moments to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted successfully for PSG to complete a 4-1 penalty win.
The record champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the last 13 seasons.
