PSG has now secured the prestigious cup on 14 separate times.
The Parisian giants required a dramatic equaliser followed by a perfect spot-kick decider to get past Marseille in Kuwait and capture a fourth straight French Super Cup title.
The European champions appeared to be sailing towards a comfortable triumph in the match between the French league winners and the Coupe de France winners after the French winger opened the net early on.
However, the southern French side fired twice late to take a shock advantage. First, Mason Greenwood converted from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of events, the Portuguese striker snatched a vital equaliser in the dying moments to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all converted successfully for PSG to seal a 4-1 penalty victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this competition for the twelfth time in the past 13 seasons.
