PSG has now claimed the prestigious trophy on 14 separate times.
Paris Saint-Germain needed a stoppage-time leveler followed by a perfect spot-kick decider to get past Marseille in Kuwait and capture a fourth straight French Super Cup title.
The Champions League holders appeared to be sailing towards a comfortable triumph in the showdown featuring the French league winners and the French Cup holders after the French winger found the net in the opening stages.
However, Marseille struck twice late to take a shock lead. Initially, the English forward converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a vital leveler in the dying seconds to send the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all scored with composure for Paris Saint-Germain to complete a convincing penalty win.
The record champions PSG, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this competition for the 12th time in the past thirteen seasons.
