PSG has now secured the prestigious trophy on 14 separate occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect penalty shootout to overcome Marseille in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting 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, Marseille fired two times late to take a shock advantage. Initially, the English forward converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos snatched a vital leveler in the dying seconds to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, saving decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted successfully for PSG to complete a 4-1 shootout victory.
The record winners PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the past thirteen years.