PSG has now secured the prestigious trophy on 14 different times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a straightforward win in the match between the Ligue 1 winners and the French Cup winners after Ousmane Dembele opened the scoring early on.
However, the southern French side struck two times late to seize a surprise advantage. First, the English forward scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos snatched a crucial leveler in the final moments to force the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, saving decisive kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for PSG to seal a 4-1 shootout victory.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this competition for the twelfth time in the past 13 seasons.
