This paper describes the photoelectrochemical studies on nanostructured iron doped titanium dioxide (TiO2) thin films prepared by sol-gel spin coating method. Thin films were characterized by X-ray diffraction, Raman spectroscopy, spectral absorbance, atomic force microscopy and photoelectrochemical (PEC) measurements. XRD study shows that the films were polycrystalline with the photoactive anatase phase of TiO2. Doping of Fe in TiO2 resulted in a shift of absorption edge towards the visible region of solar spectrum. The observed bandgap energy decreased from 3.3 to 2.89 eV on increasing the doping concentration upto 0.2 at.% Fe. 0.2 at.% Fe doped TiO2 exhibited the highest photocurrent density, similar to 0.92 mA/cm(2) at zero external bias. Flatband potential and donor density determined from the Mott-Schottky plots were found to vary with doping concentration from -0.54 to -0.92 V/SCE and 1.7 x 10(19) to 4.3 x 10(19) cm(-3), respectively. (C) 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.