In this work we are presenting the results of structural and optical investigations of TiO2 and Fe doped TiO2 films using XRD, XPS, UV‐VIS transmittance spectroscopy, and the application of these films in photocatalysis is demonstrated. Fe‐doped TiO2 films were prepared by sol‐gel method. The concentration of Fe utilized for doping ranged from 0.5 to 4% by atomic weight. For lower concentrations of Fe the transformation from amorphous‐to‐polycrystalline occurred at 400 °C. However, as the Fe concentration was increased to 4% this transformation occurred only after annealing at 600 °C. The average grain size for 4% Fe doped sample was in the range of 13 nm. In the case of pure TiO2 the XPS analysis showed only the presence of Ti 4+, where the 4% Fe doped film showed the presence of two species of Ti atoms; one of unperturbed Ti atoms and another of negatively charged surface of Ti atoms due to the interaction with Fe atoms in the anatase lattice of TiO2. The optical band gap was found to decrease with Fe concentration. The resistivity was found to decrease by one order after doping. The 4% Fe doped TiO2 films showed an increased photocatalytic activity. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)