The home side were without Sergio Ramos and Cristiano Ronaldo through suspension and Raphael Varane had not recovered from injury, meaning Casemiro had to fill in at centre back and Marco Asensio got a starting place on the left-wing.
Before the game Madrid showed off the La Liga, UEFA Super Cup and Spanish Super Cup trophies in front of the home crowd but Marcelino's side was clearly not intimidated, as they earned an impressive point at the Bernabéu.
Real Madrid started brightly with a large share of possession in the opening minutes. The deadlock was broken with the first attempt on goal from either side after 10 minutes.
Geoffrey Kondogbia lost the ball to Marco Asensio in midfield and the Real Madrid starlet advanced to the edge of the box before calmly finding the bottom-right corner with a brilliant finish, leaving Neto unmoved in the goal.
Valencia then responded eight minutes later with a well-worked effort and their first shot on target. A low cross in from the left by Toni Lato found Carlos Soler who had drifted into the box unmarked and the midfielder was able to tap home from close range, after Casemiro, the makeshift centre-back, had lost track of him.
Following the surprise equaliser, Madrid continued to apply pressure as the visitors struggled to break out of their own half but Marcelino’s men looked to be defending well.
Before the referee brought an end to the first half, Benzema was presented with two excellent chances to restore his side’s lead, but the Frenchman blasted over from close-range from a great Gareth Bale low cross and headed wide from a looping ball into the box by Toni Kroos.
At the start of the second period the away side were unlucky not to be awarded a penalty, after Gaya collided with Casemiro in the box, but nothing was given.
As the half progressed Madrid started to turn up the heat and Neto was certainly the busier of the two goalkeepers, keeping out a long-range Casemiro effort and getting down well to palm away a low drive from Luka Modric.
However, it was the visitors who took a shock lead after 77 minutes. On his debut for Valencia, Kondogbia got on the end of a stab towards the box from Rodrigo and poked the ball under Keylor Navas to put his new side ahead, with the home side's defending once again leaving much to be desired.
The lead didn't last long though as five minutes later Asensio once again stepped up for the Spanish champions. He curled in a free-kick from the edge of the box after Kovacic was tripped by Rodrigo to bring Madrid back into the game.
What followed was one-way traffic as Madrid tried to find the winner. Benzema somehow shot wide from just outside the six-yard box after an Asensio shot was blocked and fell right at his feet.
The hosts must've known it wasn't going to be their day when a powerful header by Benzema was saved onto the post by Neto in the dying moments of the game.
Valencia managed to hold on until the final whistle to secure what will be a memorable result for Marcelino's side as they showed great desire and discipline to secure the draw at the home of the European champions and continue their positive start to the season.
Meanwhile, Marco Asensio followed up on his goals in both legs of the Spanish Super Cup and continues to show why he is one of the most talked-about young players on the planet at the moment. Real Madrid will be keen for him to sign a new contract as soon as possible to stop any talk of a possible move away from the Spanish capital.