The 26-year-old Italian surged clear with just over 2km remaining and finished four seconds ahead of the peloton to record his first professional victory.
Simone Cadamuro led the bunch home just ahead of Wouter Weylandt with his Quick Step team-mate Tom Boonen retaining the overall lead.
A group of approximately 90 riders finished nearly a minute behind after a touch of wheels in the middle of the peloton with around 13km remaining that saw several men hit the ground.
Eneco Tour
Schumacher wins after crash
23/08/2006 AT 15:29
After a lively start to the 195km stage from s'Hertogenbosch in which a whole host of riders tried to escape, Spaniard Luis Pasamontes of the Unibet team seemingly made the break of the day after 58km and built up a lead of nearly ten minutes.
But he was disqualified for jumping a red light at a railway crossing and Carlos Zarate Fernandez (Saunier Duval), Paul Martens (Skil-Shimano) and Carlos Abellan (Astana-Würth) surged clear with just over 60km left.
They were over three minutes clear at one point but the circuit around the southern Dutch city took its toll and their escape ended with 20km still to race.
The stage looked set for Boonen to record back-to-back stage victories but the man from Bolzano had other ideas and he is now just one second behind the world champion on the general classification.
He said afterwards: "I have been feeling good since June. I was in good shape in the Tour de France and I'm in good shape here.
"When I saw there were just 40 riders on the last lap and that everybody was tired with no team able to push the pace along I decided to attack.
"I really needed a victory as I have been close to winning so many times that I was worried I had forgotten how to win. I needed confidence and was prepared to risk a little more to go for the win.
"I have always raced well in Holland and Belgium. I like the way they race here. I think I'm in good shape so I'll try to do my best and finish as high up the general classification as possible."
Eneco Tour
David Kopps it
22/08/2006 AT 15:10
Eneco Tour
Hincapie sitting pretty
22/08/2006 AT 11:32