The Parisian club has now secured the prestigious trophy on fourteen separate occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in Kuwait and secure a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a comfortable win in the match featuring the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele found the net in the opening stages.
Yet, the southern French side struck twice late to seize a shock advantage. Initially, the English forward converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos snatched a crucial equaliser in the dying seconds to send the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping crucial attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to complete a convincing shootout win.
The record champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this competition for the 12th time in the last 13 seasons.
