PSG has now won the prestigious trophy on 14 different occasions.
The Parisian giants needed a stoppage-time equaliser followed by a perfect penalty shootout to overcome Marseille in the Gulf and capture a fourth straight French Super Cup title.
The Champions League holders appeared to be sailing towards a comfortable triumph in the match featuring the French league winners and the French Cup winners after the French winger found the net early on.
However, the southern French side struck two times in the closing moments to take a surprise advantage. Initially, Mason Greenwood converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker snatched a vital equaliser in the dying moments to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, stopping crucial attempts from Matt O'Riley and Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to seal a 4-1 penalty victory.
The record winners PSG, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this competition for the 12th time in the past 13 years.
