PSG has now claimed the season-opening trophy on fourteen different occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect penalty shootout to get past Marseille in Kuwait and secure a record-extending fourth consecutive Trophee des Champions title.
The European champions seemed to be sailing towards a straightforward triumph in the match featuring the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele opened the net early on.
However, Marseille fired twice late to take 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 breathtaking turn of fortune, the Portuguese striker grabbed a crucial leveler in the dying moments to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to complete a 4-1 penalty win.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the past 13 seasons.