PSG has now claimed the prestigious trophy on 14 different times.
The Parisian giants needed a dramatic equaliser followed by a successful spot-kick decider to overcome Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be sailing towards a comfortable win in the match featuring the Ligue 1 champions and the Coupe de France holders after the French winger found the scoring early on.
Yet, Marseille fired twice late to seize a surprise advantage. First, the English forward converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos snatched a crucial equaliser in the dying moments to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for PSG to complete a convincing shootout victory.
Now 14-time winners PSG, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this competition for the twelfth time in the past 13 years.
