PSG has now won the prestigious trophy on 14 different times.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in the Gulf and capture a record-extending fourth consecutive Trophee des Champions title.
The European champions appeared to be coasting towards a comfortable triumph in the match featuring the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele found the net in the opening stages.
However, the southern French side fired twice in the closing moments to take a surprise lead. Initially, Mason Greenwood converted from the spot-kick, before the defender unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of events, the Portuguese striker snatched a vital equaliser in the dying moments to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, saving crucial kicks from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to complete a 4-1 shootout victory.
The record champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the last 13 years.
