PSG has now claimed the season-opening trophy on fourteen different occasions.
The Parisian giants needed a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be coasting towards a comfortable win in the match between the French league champions and the Coupe de France holders after the French winger found the scoring early on.
However, the southern French side fired twice in the closing moments to seize a surprise advantage. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker snatched a vital leveler in the dying moments to send the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, stopping crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all converted successfully for PSG to seal a 4-1 penalty victory.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this competition for the 12th time in the past 13 years.
