PSG has now won the season-opening cup on 14 different occasions.
The Parisian giants needed a dramatic equaliser followed by a successful spot-kick decider to overcome Marseille in Kuwait and capture a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be sailing towards a comfortable triumph in the match featuring the French league champions and the French Cup winners after the French winger opened the scoring in the opening stages.
Yet, Marseille fired twice in the closing moments to take a shock advantage. Initially, Mason Greenwood scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of events, the Portuguese striker snatched a vital equaliser in the final moments to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to seal a 4-1 penalty win.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the past 13 seasons.
