PSG has now claimed the season-opening cup on fourteen different occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect penalty shootout to get past Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders appeared to be coasting towards a straightforward triumph in the showdown featuring the Ligue 1 champions and the French Cup holders after the French winger opened the scoring in the opening stages.
Yet, Marseille struck two times late to seize a surprise advantage. Initially, Mason Greenwood converted from the spot-kick, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker grabbed a vital equaliser in the dying moments to send the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, saving crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted with composure for Paris Saint-Germain to complete a 4-1 penalty win.
The record winners PSG, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the past 13 years.