PSG has now won the prestigious trophy on fourteen different times.
Paris Saint-Germain required a stoppage-time leveler followed by a successful penalty shootout to get past Marseille in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders appeared to be coasting towards a comfortable win in the match between the Ligue 1 champions and the Coupe de France holders after the French winger found the scoring in the opening stages.
Yet, Marseille fired two times in the closing moments to seize a shock lead. First, Mason Greenwood converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a vital equaliser in the final moments to force the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, saving decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for PSG to complete a 4-1 penalty victory.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this competition for the twelfth time in the past 13 seasons.