The home side struggled to hold on to their lead in the closing stages of the game, but eventually bagged the full three points
The Eindhoven side dominated proceedings in the opening 45 minutes of the game and deservedly grabbed the lead via Tim Matavz at the half-hour mark. Belgian winger Dries Mertens then doubled his side's lead after the interval, before Mike Havenaar pegged one back late on. Nevertheless, Stanislav Manolev put the match to bed well into stoppage time.
Vitesse started the match the better side of the two and came close to opening the scoring in the third minute. Marco van Ginkel's shot after a superb pass from Stanley Aborah beat PSV goalkeeper Andreas Isaksson, but Marcelo cleared the ball before it passed the goalline.
Georgian youngster Giorgio Chanturia then got a chance after dispossessing Stanislav Manolev, but his left-footed shot went wide at the far post.
PSV went 1-0 up in the 31st minute after a good individual action from Zakaria Labyad. The Moroccan youngster went past two opponents before unleashing a powerful long range strike. Vitesse glovesman Piet Velthuizen failed to hold on to the shot, and Tim Matavz tapped home the rebound from five yards out.
The guests almost restored parity only minutes after the start of the second half via Alexander Buttner. Chanturia set up the wing-back on the edge of the area and he hit the post with a superb shot.
Kevin Strootman then tried his luck with a shot from about 20 yards that sailed only just over the bar, before Dries Mertens netted PSV's second. A long ball from Manolev ended up in the feet of the Belgian winger, and Mertens found the net with a stunning strike in the top corner.
Vitesse didn't give up though and pegged one back in the closing stages of the game. Renato Ibarra went past his opponent down the right before sending in a good cross for substitute Mike Havenaar, who headed home from inside the area.
Things were not meant to be though for the Arnhem side as Manolev restored PSV's two-goal lead with a calm finish well into stoppage time after a one-two with Matavz.
The Eindhoven giants have gone top of the table following their win over Vitesse with 41 points from 19 games. PSV's next encounter is Thursday's KNVB Beker clash with NEC.
Vitesse are the Eredivisie's number eight at the moment with 29 points from 19 matches. Their next game is the KNVB Beker quarter-final versus Heerenveen on Tuesday.