PSG has now secured the season-opening cup on fourteen different times.
The Parisian giants required a stoppage-time leveler followed by a successful penalty shootout to get past Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be sailing towards a comfortable triumph in the match between the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele found the net early on.
However, the southern French side struck two times late to seize a shock advantage. Initially, Mason Greenwood converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a crucial leveler in the final seconds to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, saving decisive attempts 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 convincing penalty win.
Now 14-time winners PSG, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this trophy for the 12th time in the past thirteen years.