The Parisian club has now secured the season-opening trophy on 14 different times.
The Parisian giants required a stoppage-time leveler 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 seemed to be sailing towards a straightforward win in the showdown featuring the French league champions and the French Cup winners after the French winger opened the net in the opening stages.
Yet, Marseille fired twice late to take a surprise lead. First, the English forward scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of events, the Portuguese striker grabbed a vital leveler in the dying seconds to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping decisive kicks 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 seal a 4-1 penalty win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the past 13 years.
