PSG has now secured the prestigious trophy on fourteen separate occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful penalty shootout to get past Marseille in the Gulf and capture a fourth straight Trophee des Champions title.
The European champions appeared to be coasting towards a comfortable triumph in the match between the Ligue 1 winners and the Coupe de France holders after the French winger opened the net in the opening stages.
However, the southern French side struck twice late to seize a surprise lead. First, the English forward converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a vital equaliser in the final moments to force the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored successfully for Paris Saint-Germain to seal a 4-1 shootout win.
The record winners PSG, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this competition for the 12th time in the last thirteen years.
