PSG has now claimed the season-opening cup on 14 different occasions.
The Parisian giants required a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be coasting towards a comfortable triumph in the match between the Ligue 1 champions and the Coupe de France winners after the French winger opened the scoring in the opening stages.
However, Marseille fired twice in the closing moments to seize a shock lead. Initially, the English forward scored 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, the Portuguese striker snatched a crucial equaliser in the dying seconds to force the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping crucial kicks from O'Riley and Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all converted with composure for Paris Saint-Germain to seal a 4-1 shootout win.
The record champions PSG, 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 last thirteen seasons.
