Ji-Sung Park buried a free header after eight minutes while the hugely impressive Arjen Robben, a pacy left winger, grabbed a deserved goal for his performance two minutes from time.
PSV had the best of it with the pace of Arjen Robben a constant threat alongside a stream of of crosses from Dennis Rommedahl from the right in the first half.
Robben's pace and directness caused havoc as early as the sixth minute, a driving run and low shot that Kasey Keller did well to divert.
Kezman should have done better from Robben's corner and Keller saved superbly to deny the Serbia-Montenagran striker from closer range.
However, the goal came from the corner, a free header powered home off the post by Ji-Sung Park.
Chris Perry almost levelled after 23 minutes when his looping header clipped the crossbar but Kezman then had three further chances in a short spell as he first failed to connect with Rommedahl's cross, then scissor kicked into Row Z and then missed the target with a free header.
Postiga flashed wide from 18 yards and, just before the break, Waterreus did well to hang onto a tricky, dipping Redknapp free-kick.
The second half succumbed to more traditional pre-season fayre with substitutions affecting the flow of the game.
Robben was instrumental in a couple of early PSV chances, Van Bommel shooting wide from 20 yards, Kezman blasting over from 12 yards.
Rohan Ricketts, who came on for Davies at the end of the first half, looked lively in patches while Poyet, on for Acimovic, flicked a header wide.
Poyet almost created something from Taricco's cross and set-up Dean Marney's strike just wide from 25 yards.
But PSV had the last word as Robben turned away from two challenges, had his shot blocked by Perry but was left with the simple task of tapping into an empty net with Keller stranded.
MINUTE BY MINUTE GUIDE
2mins: Ji-Sung Park sliced volley over from corner.
6mins: Robben pacy run into box and low show saved well by Keller.
7mins: Kezman header straight at Keller from Robben's corner, should have done better.
8mins: Rommedhal break, Kezman clear in front of goal but Keller spread himself to save well.
8mins: GOAL. From corner, free header from Ji-Sung Park in off post. 0-1.
23mins: WOODWORK. Perry's looping header from Taricco's cross clipped off the crossbar.
25mins: Kezman somehow failed to connect with Rommedhal cross from right.
29mins: Kezman acrobatic attempt from Rommedhal cross, skied it into Row Z.
33mins: Another free header from a corner, this time Kezman missed target.
34mins: Acimovic created something out of nothing down left, deep cross volleyed over by Keane.
38mins: SUB. Ricketts for Davies.
42mins: Postiga half-a-yard in the box, closed down by two defenders, flashed shot wide.
45mins: Waterreus good hands to deal with dipping Redknapp free-kick.
Half-time: Spurs 0-1 PSV
Half-time: Bunjevcevic for Anderton.
47mins: Robben dart inside, ball fell to Van Bommel, shot a yard wide from 20 yards.
51mins: Robben into Kezman who shot over from 10 yards.
59mins: Keller quick dash out to deny Kezman.
61mins: SUB: Poyet for Acimovic.
65mins: Ricketts spread play well from right to left, Taricco cross flicked wide by Poyet under pressure.
75mins: SUB. Marney for Redknapp.
78mins: Keane free-kick from 22 yards always curling over.
83mins: Poyet in amongst it from Taricco's dink but ball fell kindly for PSV.
86mins: Marney drive wide after Poyet laid ball to him.
88mins: GOAL. Robben break after Spurs attack broke down, cut inside two players, initial effort blocked by Perry but Robben tapped rebound into empty net. 0-2.
Starting line-ups: Spurs: Keller, Carr, Taricco, Gardner, Perry, Redknapp (Marney, 75), Anderton (Bunjevcevic, 45), Davies (Ricketts, 38), Acimovic (Poyet, 61), Postiga, Keane.
PSV: Waterreus, Begelund, Hofland (Vogel, 45), Colin, Young-Pyo Lee, Van Bommel, ver der Schaaf, Ji-Sung Park (de Jong, 74), Rommedahl (Hoogstrate, 45), Kezman, Robben.
A goal in each half secured Dutch champions PSV Eindhoven a pre-season friendly win at White Hart Lane on Sunday.