Hernandez also hit the post in a cameo spell which lit up an effective but otherwise uninspiring Manchester United display.
United, missing several key players includingWayne Rooney, were able to name Rio Ferdinand and Michael Carrick in their line-up, while Sir Alex Ferguson opted for Anderson in the centre of midfield.
The away side seemed to settle well and the in-form Dimitar Berbatov struck a fierce early effort from distance which was close to finding the top corner.
The better chances fell to Valencia, however.
In a frenzied two minute spell Pablo pounced on a moment of indecision from Carrick to flash a shot from range narrowly over the bar, and then Roberto Soldado contrived to miss an open goal when Edwin Van der Sar missed a cross.
Soldado looked on aghast as his header looped over the crossbar.
Anderson nearly got on the end of Nani's cross from the right shortly afterwards, but in truth there was little in the way of clear-cut opportunities to score.
Both sides exercised caution as the game's bright opening ebbed away, and little changed as the second half started.
Berbatov, who had a lonely evening leading the line, fashioned a chance for himself brilliantly from the left wing ,drawing a save from Cesar Sanchez, but it was an isolated moment.
Coach Unai Emery stirred the home fans into song with his decision to bring on Aritz Aduriz on the hour and turn to a more attacking formation.
His introduction seemed to lift the side and Valencia looked the likelier to find the winner as the game entered its final stages.
Full-backs Miguel and Jeremy Mathieu probed on the wings, while Soldado and Aduriz were a handful which forced Rio Ferdinand and Nemanja Vidic, playing together for the first time this season, to be at their sharpest.
United fans must have thought their best chance of a smash-and-grab victory had disappeared when Nani's cross was met by Hernandez's outstretched boot and steered on to the post after 83 minutes.
But just two minutes later Federico Macheda, on the field himself for less than 60 seconds, slid a pass across to the Mexican who eased past David Navarro before clinically striking the ball into the corner of the goal.
Valencia grew frustrated as the final minutes slipped away, and left the field without anything to show for their efforts.
It will not concern United, though, who will be delighted by the clean sheet and a first win away in Spain for over eight years - a victory that puts them top of the group, level with Rangers.
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