PSG has now won the prestigious trophy on fourteen different times.
The Parisian giants needed a dramatic equaliser followed by a successful spot-kick decider to get past Marseille in Kuwait and capture a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a straightforward win in the match featuring the Ligue 1 champions and the Coupe de France holders after the French winger opened the net in the opening stages.
Yet, Marseille fired two times late to take a surprise advantage. First, the English forward converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker snatched a crucial leveler in the dying moments to force the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, saving crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to complete a 4-1 penalty victory.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the last thirteen years.
