PSG has now secured the season-opening trophy on 14 different occasions.
The Parisian giants required a dramatic leveler followed by a perfect penalty shootout to get past Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be sailing towards a comfortable win in the match between the Ligue 1 winners and the French Cup winners after Ousmane Dembele opened the scoring in the opening stages.
However, the southern French side struck twice late to seize a surprise advantage. First, the English forward scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable twist of events, the Portuguese striker grabbed a crucial equaliser in the dying seconds to send the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, saving decisive attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted successfully for PSG to complete a 4-1 shootout win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this competition for the 12th time in the past 13 seasons.