- Érick Gutiérrez (48')
- Cody Gakpo (50')
- Ryan Gravenberch (23')
Mexico international Erick Gutierrez equalised with a diving header in the 48th minute, stealing in unmarked at the back post to get on the end of a flick-on from a free kick.
Cody Gakpo then claimed the winner two minutes later with a strong run from deep and a powerful shot that caught out Ajax's veteran goalkeeper Maarten Stekelenburg, who was preferred in the lineup to the departing Andre Onana.
PSV, who are four points behind Ajax in the Eredivisie standings with five rounds to complete, also had an early effort ruled out by VAR while Ajax had two tight offside decisions go against them.
It was PSV's first cup success in 10 years, denying Ajax a third successive Dutch Cup final win under coach Erik ten Hag, who is the leading candidate to join Manchester United next season.
- Danny Makkelie