PSG has now secured the season-opening trophy on fourteen separate occasions.
The Parisian giants needed a stoppage-time equaliser followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be sailing towards a straightforward win in the showdown between the French league champions and the Coupe de France holders after the French winger opened the net early on.
However, Marseille fired twice in the closing moments to take a surprise lead. Initially, the English forward scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a crucial leveler in the dying seconds to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for PSG to seal a 4-1 shootout victory.
The record champions PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the past thirteen years.
