By varying the formation voltage and time length during the anodizing process, the morphology of the TiO2 film obtained was considerably modified varying their inner diameter from around 38 nm to 82 nm, and their length from around 0.9 μm to 3.8 μm. Furthermore, the optical and semiconducting properties of TiO2 films were also modified with the processing variables; this behavior was attributed to the insertion of species in the electrolyte in the TiO2 lattice during their growth. However, the photoelectrochemical performance toward water oxidation of the TiO2 only showed to be dependent with the inner diameter of the nanotubes, that could be related to the interaction of the film with the light and the transport of species in the electrolyte inward or outward the film.