The Parisian club has now won the season-opening trophy on 14 different times.
The Parisian giants needed a dramatic equaliser followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The Champions League holders appeared to be coasting towards a comfortable triumph in the match between the French league winners and the French Cup winners after the French winger found the net in the opening stages.
However, Marseille struck two times in the closing moments to seize a shock advantage. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of events, the Portuguese striker grabbed a crucial leveler in the final seconds to force the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for PSG to complete a convincing penalty victory.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the past thirteen seasons.
