The Parisian club has now claimed the season-opening trophy on fourteen separate occasions.
The Parisian giants required a dramatic equaliser followed by a successful spot-kick decider to get past 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 match featuring the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele found the scoring early on.
However, the southern French side fired twice in the closing moments to seize a shock advantage. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a crucial equaliser in the final moments to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for PSG to seal a convincing penalty victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this competition for the 12th time in the past 13 seasons.
