PSG has now won the prestigious trophy on 14 separate occasions.
The Parisian giants needed a stoppage-time equaliser followed by a perfect penalty shootout to get past Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a comfortable triumph in the match featuring the French league champions and the French Cup holders after Ousmane Dembele opened the scoring early on.
Yet, the southern French side struck twice in the closing moments to seize a shock advantage. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of events, Goncalo Ramos snatched a vital equaliser in the dying seconds to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to seal a 4-1 shootout victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this competition for the 12th time in the past 13 years.
