The visitors from Barcelona opened the scoring after just three minutes when Jhon Cordoba collected a loose ball outside the box and slammed home into the top corner.
However, Los Che restored parity just four minutes later, with Paco Alcacer running into the Espanyol box and finding the target from close range.
However, the two sides went in at the break locked at 2-2 as Sergio Garcia equalised for Espanyol on the stroke of half time.
Cordoba was brought down by Jeremy Mathieu inside the Valencia box and Garcia made no mistake from the resulting spot kick.
The end-to-end action continued in the second half with both Valencia and Espanyol creating a number of chances to add to the scoreline, but they had to settle for a share of the spoils.