The Dutch lost holding midfielder Nigel de Jong to injury inside the first 10 minutes and Mexico soon had a dominant spell.
Hector Herrera dragged a shot wide before he appeared to be denied the ball in the penalty area by high foots from both Ron Vlaar and Stefan de Vrij. Mexico appealed for a penalty, but Portuguese referee Pedro Proenca didn't agree.
The hot and humid conditions in Fortaleza meant that one cooling break was allowed per half to allow the players to take on fluids.
Three minutes before the interval Giovani dos Santos was presented with a shooting opportunity from a tight angle but couldn't get the better of Jasper Cillessen.
Netherlands then wanted a penalty of their own when Arjen Robben seemed to be taken out by a combination of Rafael Marquez and Hector Moreno in the area, but once again Proenca opted against pointing to the spot.
Mexico broke the deadlock just three minutes after the resumption when Dos Santos rifled a bouncing ball low into the corner from 25 yards.
The Dutch came within of inches of an equaliser just before the hour mark when De Vrij volleyed at goal from inside the six-yard box but was somehow denied by the strong hands of Guillermo Ochoa, who managed to palm the ball agains the inside of the post.
Moments later it was Wesley Sneijder to go close. The Galatasaray man was fed by Robben but had his shot deflected up and inches over the crossbar.
With 15 minutes on the clock, Robben had his clearest sight of goal when he glided into the box but couldn't beat Ochoa from a tight angle.
It looked like the Dutch would go out in the first knockout stage after winning every single group game until Sneijder struck with two minutes of normal time remaining.
A loose ball fell his way from a corner and he kept his cool to slam a volley low into the corner.
Oranje then sent Mexico home with an injury-time penalty from substitute Klaas-Jan Huntelaar after Robben had been brought down in the box by Marquez.
Louis van Gaal's side will next face the winner of tonight's match between Costa Rica and Greece in the quarter-finals on Saturday afternoon.
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