The effect of thermal treatment on TiO2 thin films under oxygen deficient environment (5% H2 in Ar) at partial pressure of 2 x 10(-2) Torr have been studied for photoelectrochemical (PEC) water splitting application. Thermal treatment in anatase TiO2 thin films exhibits a shift in optical absorption from UV to visible region and activates TiO2 for water splitting application under visible light. X-ray photoelectron spectroscopy results showed that the thermal treated thin films contain oxygen vacancies, which suggests improved charge transport. Optical absorption, X-ray spectroscopy (XPS) and Kelvin probe force microscope (KPFM) studies show reduction in band gap by 0.36 eV, shift in valence band maximum by 0.49 eV towards the Fermi level and work function values by 0.3 eV towards the vacuum level. The pristine TiO2 thin films exhibit very less photoactivity in terms of photocurrent density, whereas thermally treated thin films displayed a markedly enhanced photocurrent density of similar to 2.41 mA/cm(2) at 0.23 V vs. Ag/AgCl. Higher values of photocurrent density in thermal treated TiO2 films have been explained in terms of change in the optical and electrical properties along with energy band diagram. 2016 Elsevier B.V. All rights reserved.