PSG has now secured the season-opening cup on 14 different times.
The Parisian giants needed a dramatic leveler followed by a perfect spot-kick decider to overcome Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be coasting towards a straightforward triumph in the showdown featuring the Ligue 1 champions and the French Cup holders after the French winger opened the net in the opening stages.
Yet, Marseille struck twice late to take a shock advantage. First, the English forward scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a vital equaliser in the dying seconds to force the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, saving decisive kicks from O'Riley and Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to complete a 4-1 penalty victory.
Now 14-time champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the 12th time in the last thirteen seasons.