PSG has now secured the prestigious trophy on 14 different times.
The Parisian giants needed a dramatic equaliser followed by a perfect penalty shootout to get past Marseille in Kuwait and capture a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a comfortable win in the match featuring the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the net in the opening stages.
However, the southern French side fired two times in the closing moments to seize a shock lead. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a vital equaliser in the dying seconds to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for PSG to seal a convincing penalty win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the last thirteen years.
