A late goal from the Slovenian dealt a huge blow in the Alkmaar side's title aspirations, and could find themselves six points off the league summit by the end of the week
Jeremain Lens handed the hosts an early lead, before goals from Jozy Altidore and Roy Beerens put the visitors ahead before the break. A late goal from Lens drew the sides level, before a last-second winner from Tim Matavz handed PSV the win.
Having fallen to a 2-1 defeat away to RKC last time out, the home side needed a win to stay within reach of Ajax. The visitors trailed the table-toppers by just three points, but the Amsterdam side’s superior goal difference meant it would take an unlikely margin of victory to pip them to top spot.
PSV started the match with attacking intentions and Dries Mertens registered the first attempt on target, testing Esteban with an early shot. The keeper was called into action again minutes later, with deputy left-back Jetro Willems unleashing a thunderous effort after charging past Etienne Reijnen.
The home side were rewarded for their verve in the 17th minute, taking the lead courtesy of some woeful goalkeeping from Esteban. Lens sent a fairly timid shot towards goal, which somehow found its way to the back of the net after the shot-stopper mistimed his collection.
AZ responded just six minutes later, levelling matters through a spectacular effort from Altidore. The American was gifted acres of space some 30 yards out, and left Przemyslaw Tyton helpless with a fierce shot into the top corner.
Beerens should have put the visitors ahead in the 27th minute, failing to convert a glorious chance with only the keeper to beat. The PSV defence was easily exposed as the Dutchman was put through on goal, but an intervention at point-blank range from the Pole kept his side in the game.
Beerens would not be denied his third goal of the season, however, firing his side into the lead 34 minutes in. A simple link-up play with Maarten Martens allowed the winger to unleash a piledriver past an exposed Tyton, clattering the inside of the post on the way in.
The second half unfolded in more timid fashion, with neither side allowed an early sight of goal. A long-range effort from Martens flew well wide, before the anonymous Mertens saw his attempt roll into the side netting at the other end. Crisp play off a corner then allowed Zakaria Labyad to fire at goal, but a deflection sent the ball to safety.
Chances were squandered at both ends later on, with both sides lacking any sort of rhythm. Ola Toivonen failed to convert from six yards out, before a collective effort from Timothy Derijck and Tyton denied Charlison Benschop a goal.
PSV would find an equaliser in the 76th minute, with Lens drawing his side level with his second of the night. The Dutchman did well to control a long ball from Memphis Depay, before firing home past a charging Esteban.
The hosts went in avid search for a winner late on, and found a last-minute breakthrough via Matavz. A tussle in the AZ box saw the ball fall to the Slovenian, who gratefully converted with seconds of extra-time remaining.
AZ consequently remain three points behind league leaders Ajax, with the reigning champions set to play on Sunday.
PSV climbed to third spot in the table for now with 57 points from 30 games. The Eindhoven side resume Eredivisie action at home against NEC on April 22.