The Parisian club has now claimed the prestigious trophy on 14 different times.
The Parisian giants needed a stoppage-time equaliser followed by a successful penalty shootout to overcome Marseille in the Gulf and secure a record-extending fourth consecutive Trophee des Champions title.
The Champions League holders appeared to be coasting towards a straightforward win in the showdown featuring the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele opened the net early on.
However, the southern French side fired two times in the closing moments to take a surprise advantage. Initially, the English forward scored from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking turn of events, the Portuguese striker grabbed a vital equaliser in the final moments to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, stopping crucial attempts from O'Riley and Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for PSG to seal a 4-1 penalty victory.
The record winners PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the last thirteen years.
