A first-half hat-trick from Luuk de Jong helped PSV canter to a victory that moved them up to second place on 11 points from their opening five matches of the new campaign.
Ajax are two points clear at the top after coming from two down to draw 2-2 at Twente Enschede.
Troubled Twente, who sacked their coach Alfred Schreuder a fortnight ago and have yet to appoint a replacement, looked set for a first win of the season after goals from Felipe Gutierrez and Hakim Ziyech put them in a commanding position.
But Viktor Fischer and Nemanja Gudelj hit back to maintain Ajax's unbeaten start.
De Jong blasted home his hat-trick inside the opening 41 minutes.
Substitute Jurgen Locadia netted two more after the break and Davy Proepper was also on the scoresheet in a morale-boosting performance before Manchester United's visit on Tuesday.
Lars Veldwijk also grabbed a hat-trick as PEC Zwolle beat Excelsior 3-0 to go third behind PSV on goal difference.
Roda JC Kerkarde are a point further back after a goalless draw with fellow promoted team NEC Nijmegen.
A double from Norwegian import Markus Henriksen helped AZ Alkmaar secure their first victory of the season in a 3-1 win away at De Graafschap, who have now lost all of their opening five games.
(Reporting by Mark Gleeson; Editing by Toby Davis)
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