PSG has now secured the season-opening cup on 14 separate times.
The Parisian giants needed a dramatic leveler followed by a successful spot-kick decider to get past Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be sailing towards a comfortable win in the match between the French league champions and the French Cup winners after the French winger found the scoring in the opening stages.
However, the southern French side struck two times late to take a surprise lead. First, the English forward converted from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a vital leveler in the final seconds to force the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for PSG to complete a 4-1 shootout win.
The record winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this trophy for the twelfth time in the last thirteen seasons.
