The Parisian club has now claimed the prestigious cup on fourteen different occasions.
The Parisian giants needed a dramatic leveler followed by a perfect spot-kick decider to get past Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be sailing towards a straightforward win in the match featuring the Ligue 1 winners and the French Cup holders after the French winger opened the scoring early on.
Yet, the southern French side struck two times in the closing moments to take a surprise lead. First, the English forward converted from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of fortune, the Portuguese striker snatched a crucial equaliser in the final seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, stopping decisive attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted successfully for PSG to complete a 4-1 penalty victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this trophy for the twelfth time in the last 13 years.