PSG has now won the season-opening cup on 14 separate times.
The Parisian giants required a stoppage-time leveler followed by a perfect penalty shootout to overcome Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be sailing towards a straightforward triumph in the match between the Ligue 1 champions and the Coupe de France winners after the French winger found the scoring early on.
However, the southern French side struck two times in the closing moments to seize a surprise lead. Initially, the English forward converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos snatched a vital equaliser in the dying moments to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, stopping crucial kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to complete a convincing shootout 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 won this competition for the 12th time in the last 13 years.
