The Parisian club has now won the prestigious cup on 14 separate times.
The Parisian giants needed a stoppage-time leveler followed by a perfect spot-kick decider to get past Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be sailing towards a comfortable win in the showdown between the French league champions and the Coupe de France holders after the French winger opened the scoring in the opening stages.
However, Marseille struck twice late to take a surprise advantage. First, the English forward converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a vital equaliser in the final moments to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to complete a 4-1 penalty victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this trophy for the 12th time in the past thirteen seasons.
