PSG has now won the prestigious trophy on 14 separate occasions.
The Parisian giants needed a dramatic equaliser followed by a perfect penalty shootout to overcome Marseille in Kuwait and capture a record-extending fourth consecutive Trophee des Champions victory.
The European champions seemed to be coasting towards a straightforward triumph in the match between the Ligue 1 champions and the French Cup winners after the French winger found the net early on.
Yet, Marseille struck twice late to seize 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 remarkable turn of events, the Portuguese striker snatched a crucial equaliser in the final moments to send the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all scored successfully for PSG to complete a convincing penalty win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the last thirteen seasons.
