Balazs Dzsudzsak's fifth league goal of the season settled a low-key encounter at Phillips Stadion in the hosts' favour.
The Hungary international pounced on defensive uncertainty to slot the ball past keeper Piet Velthuizen in the second half.
PSV were dominant throughout, and could have extended their lead but for a late double save by Velthuizen which denied Jonathan Reis a second goal.
Home keeper Andreas Isaksson held Claudemir's effort after a rare Vitesse attack in a lacklustre first half.
Francisco Rodriguez then headed Otman Bakkal's cross wide for the hosts as the interval arrived with the scoreline still blank.
But in the 64th minute, Danko Lazovic's cross was not properly cleared and Dzsudzsak converted from six yards.
The striker almost turned provider with 10 minutes remaining, as his cross was headed over the bar by substitute Ola Toivonen from the edge of the six-yard box.
And three minutes later, Velthuizen ensured Vitesse would limit the damage as Lazovic crossed and Reis shot from eight yards. Velthuizen saved well but had to react quickly to save again as the ball rebounded to the same player.
The result ensures PSV will finish the weekend in second place in the Eredivisie, sitting as they do four points clear of Ajax, who play Feyenoord at home tomorrow.
Vitesse languish in 13th, just a point clear of the relegation play-off places, following their third defeat in succession.