WO(3) thin films were fabricated by sol-gel method using polyethylene glycol (PEG) as dispersing agent. Physical and photoelectrochemical properties of the synthesized nanocrystalline films were studied by varying weight ratio of PEG to tungsten precursor (x). Based on AFM observations and statistical modeling of the WO(3) surface, the thickness of the films increased by increasing the amount of x with a nearly linear fashion while the surface roughness reached to a saturated value. However, the film synthesized with x = 4 showed a chaotic surface behavior. Optical analysis revealed that by increasing the x, transmittance of the films decreased while their band gap energies remained unchanged. According to XRD results, variation of x did not change structure of the nanocrystalline film while XPS analysis indicated a better stoichiometry for the films with higher x values. A less charge transport life time was obtained for films with higher x values, but an enhanced photoresponse of the films and also hydrogen production via water splitting reaction were observed by increasing the amount of x. On the other hand, the charge transfer resistance of the samples reduced from 6.5 k Omega to 1.2 k Omega by addition of PEG to the sol from x = 0 to x = 2. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.