Eredivisie wrap: Late penalty for new leaders Twente
Twente went into the match unbeaten in their past three league games - a record which looked under threat.
Steve McLaren made two changes to the Twente squad that defeated Bursaspor 4-1 in the Europa League midweek, with Felipe Gutierrez and Gyasi called in to replace Dmitri Bulykin and Willem Janssen.
Twente appeared fatigued, but Leroy Fer's 92nd minute penalty was enough to break the deadlock and preserve their 100 percent record.
The loss means VVV remain at the bottom of the table after three consecutive defeats.
Vitesse continued their impressive start to the Eredivisie season beating Feyenoord 1-0 at home with a stoppage time winner on Sunday.
Feyenoord had registered two wins and a draw in the opening three games but Wilfried Bony scored with a classy flick behind his legs in the dying moments to seal victory for Vitesse and maintain its unbeaten record in the new campaign.
The result keeps Vitesse in the top three after securing 10 points from their opening four games.
Meanwhile, defending champions Ajax played out a 2-2 draw at Heerenveen.
Thulani Serero got the ball rolling for Ajax on 13 minutes but two goals from Alfred Finnbogason before the break sent Hereenveen into the break with a half-time lead.
Serero completed his brace two minutes into the second-half but his night ended prematurely after seeing red six minutes later.
And in the battle of last season's third and fourth placed teams, PSV trounced AZ Alkmaar 5-1.
Slovenian striker Tim Matavz bagged a brace, while Mark van Bommel, Marcelo and Atiba Hutchinson added themselves to the scoresheet.