PSG has now won the season-opening trophy on fourteen separate times.
The Parisian giants required a dramatic equaliser followed by a perfect spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be sailing towards a comfortable triumph in the showdown featuring the French league champions and the French Cup holders after the French winger found the net early on.
Yet, Marseille struck two times in the closing moments to seize a shock advantage. First, the English forward 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, the Portuguese striker snatched a crucial leveler in the final seconds to force the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, saving decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for PSG to complete a 4-1 shootout victory.
The record champions PSG, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this trophy for the 12th time in the last 13 seasons.
