PSG has now claimed the prestigious cup on fourteen separate times.
The Parisian giants required a stoppage-time equaliser followed by a successful spot-kick decider to overcome their arch-rivals in Kuwait and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a straightforward win in the match featuring the French league champions and the Coupe de France winners after the French winger found the scoring early on.
However, Marseille struck twice in the closing moments 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 turn of fortune, the Portuguese striker grabbed a vital leveler in the dying seconds to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo 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 winners PSG, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this trophy for the 12th time in the past 13 seasons.
