Five goals after the break gave Vitesse a sixth straight league win and preserved a two-point lead over Ajax who thrashed NAC Breda 4-0 with a Davy Klaassen hat-trick. Third-placed Twente won 2-1 at AZ Alkmaar to stay three points off the pace.
But that lasted all of a minute as Davy Propper restored the two-goal advantage and Patrick van Aanholt added the fifth two minutes later. Propper got the sixth right at the end.
Vitesse top the standings with 33 points from 16 games while seven league matches without success has plunged PSV into further crisis as they dropped to 10th in the 18-team table.
Klaassen's treble gave Ajax a comfortable home win over Breda, prompting confident coach Frank de Boer to say: "If we keep this up we'll be champions again."
His post-match comments came as Ajax moved to 31 points after getting a major confidence boost ahead of their key Champions League clash with AC Milan on Wednesday which they must win to advance to the knockout phase.
The 20-year-old Klaassen scored twice before the interval and completed his hat-trick just after the hour mark.
Bojan Krkic netted for a second successive game to add the fourth and mark his return after two months out injured.
Twente's Youness Mokhtar conjured a stoppage-time winner to take his side to 30 points as they recovered to win at Alkmaar.
Roy Beerens was set up from the wing to give AZ the lead after three minutes but Mokhtar equalised in the 39th and snatched the late winner to inflict a first home defeat of the season on Alkmaar who are sixth on 24 points.
Fourth-placed Feyenoord, who have the same points total, visit Heerenveen on Sunday when Groningen in fifth host ADO Den Haag. Seven-placed Utrecht are also in the quartet level on 24 points after their 2-0 home win over NEC Nijmegen on Friday.
RKC Waalwijk remain stuck in the relegation zone after being held 2-2 at home by struggling SC Cambuur, for whom Michiel Hemmen scored twice in three minutes in the first half.