The Parisian club has now secured the season-opening trophy on fourteen separate occasions.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be coasting towards a straightforward triumph in the showdown featuring the Ligue 1 champions and the Coupe de France holders after the French winger opened the net early on.
Yet, the southern French side struck twice late to seize a surprise advantage. First, the English forward scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a vital leveler in the dying seconds to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored successfully for PSG to seal a 4-1 shootout win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this competition for the 12th time in the last 13 seasons.