PSG has now claimed the prestigious cup on 14 different occasions.
The Parisian giants needed a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in Kuwait and secure a record-extending fourth consecutive Trophee des Champions title.
The European champions appeared to be coasting towards a comfortable win in the match between the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele opened the scoring in the opening stages.
However, the southern French side struck twice in the closing moments to take a surprise advantage. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a vital equaliser in the dying moments to send the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all scored with composure for PSG to complete a 4-1 penalty win.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this trophy for the 12th time in the last 13 seasons.
