PSG has now secured the prestigious trophy on 14 separate times.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and secure a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders appeared to be coasting towards a comfortable win in the showdown between the French league champions and the Coupe de France winners after Ousmane Dembele found the net early on.
Yet, the southern French side struck two times late to take a shock lead. First, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker snatched a crucial leveler in the dying seconds to force the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for PSG to complete a 4-1 penalty victory.
The record winners PSG, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this competition for the 12th time in the last 13 years.
