PSG has now won the season-opening trophy on 14 separate occasions.
Paris Saint-Germain required a dramatic equaliser followed by a perfect penalty shootout to overcome Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The European champions seemed to be coasting towards a straightforward 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 seize a surprise lead. Initially, Mason Greenwood converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a vital equaliser in the final seconds to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving decisive kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to seal a 4-1 shootout victory.
Now 14-time champions PSG, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the last thirteen seasons.
