PSG has now won the season-opening cup on 14 separate occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful penalty shootout to overcome Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a straightforward triumph in the showdown featuring the French league winners and the Coupe de France holders after the French winger opened the net early on.
However, the southern French side struck two times late to take a shock advantage. First, the English forward converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a vital equaliser in the dying seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, saving crucial kicks from O'Riley and Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to seal a 4-1 shootout victory.
The record winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the last thirteen years.
