The undoped and sol-gel Fe-doped TiO2 thin films deposited by spray pyrolysis method on glass substrates, at 373 K were prepared. The influence of Fe dopant concentration and the temperature of thermal treatment on the obtained materials has been studied using: XRD, XPS, PL and TEM techniques, and measurements of hydrophilic and photocatalytic properties. A detailed XRD analysis has established the structural changes due to the thermal treatment and the dopant concentration. For the samples with the lowest Fe content, the thermal treatment of the samples at 673 K lead to an increased super-hydrophilic performance and the best yield of nitrobenzene removal from water. In order to underline the effect of iron dopant, a comparative structural study was initiated for Fe-doped TiO2 films as prepared and the sol-gel nanopowders with the same composition presented in our previous paper. All the doped materials have also been compared with the corresponding materials in the absence of the dopant (TiO2 undoped). A mechanism of photocatalytic degradation of nitrobenzene has been proposed.