Valladolid's first opening came just four minutes later when Daniel Larsson nodded a rebound towards goal from close range, but his effort was well-blocked.
Valencia almost broke the deadlock with seven minutes left of the first half as Eduardo Vargas peeled off into some space to nod an effort towards the bottom corner, drawing a fine stop from the keeper.
The visitors had another chance right on the stroke of half time but once again they couldn't make the most of it as Paco fired an effort well over the crossbar.
Paco threatened again 10 minutes after the restart when he collected a pass inside the area before drilling a low shot towards goal that Jimenez had to save.
Valencia continued to push for an opening goal and had a decent opportunity to get it with 20 minutes left as Pablo Piatti found himself with room to shoot inside the box, but he fired a powerful effort wide.
Neither side could find a winner in the closing stages as the spoils were shared, leaving Valladolid out of the bottom three on goal difference.