The Parisian club has now won the season-opening trophy on 14 different times.
The Parisian giants needed a stoppage-time equaliser followed by a perfect penalty shootout to get past Marseille in the Gulf and capture a fourth straight French Super Cup title.
The Champions League holders appeared to be coasting towards a straightforward triumph in the showdown featuring the Ligue 1 champions and the Coupe de France holders after the French winger found the scoring in the opening stages.
Yet, the southern French side struck twice late to take a surprise advantage. First, Mason Greenwood scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a vital equaliser in the dying seconds to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, stopping decisive kicks from O'Riley and Traore.
In the shootout, Ramos, the midfielder, the full-back, and the young talent all scored with composure for PSG to complete a 4-1 penalty win.
The record winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the last thirteen years.