A second-half salvo from Philip Cocu's side consigned the champions to a 4-0 defeat as Vitesse beat surprise package Zwolle
PSV went top of the Eredivisie with a crushing 4-0 home victory over champions Ajax on Sunday.
That result, combined with Zwolle's 3-0 defeat at Vitesse, means PSV have opened up a two-point lead at the top of the table.
All four of PSV's goals came in a 15-minute spree in the second half, started off by Tim Matavz in the 53rd minute.
Jetro Willems, Oscar Hiljemark and Ji-Sung Park then all found the net in quick succession as the hosts cruised to victory to maintain the only unbeaten record in the division.
Zwolle, leaders at the start of the day, were well beaten by Vitesse, who climbed to fifth.
Chelsea loanee Lucas Piazon scored twice, in the 35th and 88th minutes, either side of Kelvin Leerdam's strike midway through the second half.
Elsewhere, Tonny Vilhenna's goal in the 35th minute gave Feyenoord a 1-0 win over Utrecht as they climbed to eighth, while NAC Breda completed a quartet of home victories with a 3-0 defeat of AZ Alkmaar.
Danny Verbeek opened the scoring for NAC in the 50th minute, before Rydell Poepon doubled the lead 24 minutes later.
Elson Hooi added further gloss to the scoreline in stoppage time to seal a victory that moves NAC up to 12th in the table.