PSG has now secured the prestigious trophy on fourteen separate times.
The Parisian giants required a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be sailing towards a straightforward win in the showdown featuring the French league champions and the French Cup holders after the French winger opened the net early on.
However, the southern French side struck two times in the closing moments to take a surprise lead. First, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker snatched a crucial leveler in the dying seconds to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all converted with composure for PSG to complete a convincing penalty win.
The record champions PSG, who faced last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the last thirteen seasons.
