PSG has now won the season-opening cup on 14 separate times.
The Parisian giants needed a dramatic leveler followed by a successful spot-kick decider to overcome Marseille in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The European champions seemed to be coasting towards a comfortable triumph in the showdown between the French league winners and the French Cup holders after the French winger found the net early on.
Yet, Marseille struck twice late to take a shock lead. Initially, Mason Greenwood 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, the Portuguese striker snatched a crucial equaliser in the final moments to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all converted successfully for PSG to complete a 4-1 penalty victory.
The record champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the last thirteen seasons.
