PSG has now claimed the season-opening trophy on 14 separate times.
The Parisian giants needed a dramatic leveler followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The European champions seemed to be coasting towards a straightforward triumph in the match between the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele found the net in the opening stages.
Yet, the southern French side struck twice in the closing moments to seize a shock lead. Initially, Mason Greenwood scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a crucial leveler in the dying moments to send the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all converted successfully for PSG to complete a convincing shootout victory.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this competition for the twelfth time in the past thirteen years.
