PSV scored three times in the last 15 minutes after Heracles Almelo was reduced to 10 men for a 5-2 win that kept the Eindhoven club on top of the Eredivisie on Saturday.
Struggling powerhouse Ajax could manage only 1-1 at home to NEC Nijmegen and slipped to fourth place, dropping a point below Groningen, which beat Vitesse Arnhem 4-1 in Friday's only match.
FC Twente stayed second, behind PSV on goal difference, by beating De Graafschap Doetinchem.
Midfielder Theo Janssen scored in either half, with both strikes coming from free kicks. He opened the scoring by curling a ball around the De Graafschap wall in the 8th minute and repeated the trick in the 69th.
Everton Ramos da Silva gave Heracles the lead in Eindhoven when he headed in from close range after a cross from the right by Darl Douglas in the 27th.
The advantage lasted only nine minutes before Balazs Dzsudzsak equalized with a shot at the far post. Four minutes before halftime Dzsudzsak crossed from the left for Ola Toivonen to control the ball on his chest and fire a left-foot shot past goalkeeper Remko Pasveer.
Everton scored his second to bring NEC level in the 62nd, but the game swung PSV's way when defender Peter Reekers was sent off in the 70th for his second yellow card.
Toivonen scored his second four minutes later before Ibrahim Afellay and Marcus Berg found the net in the last two minutes.
In Amsterdam, Egypt striker Mido gave Ajax the lead in the 76th minute on a quick break after NEC hit the post of Maarten Stekelenburg's goal. Miralem Sulejmani sprinted down the right flank and crossed with the outside of his left foot for Mido to head powerfully home.
But Bram Nuytinck snatched a point for NEC just two minutes later when he fired through a crowded box after Ajax failed to clear a free kick.
"If you want to be champion you have to win games like that," Mido said. "When you're in the 80th minute and you're 1-0 and you're playing at home you can't concede goals like that."
