Iron oxide nanostructures are of particular interest because they can be used as photocatalysts in water splitting due to their advantageous properties. Electrochemical anodization is one of the best techniques to synthesize nanostructures directly on the metal substrate (direct back contact). In the present study, a novel methodology consisting of the anodization of iron under hydrodynamic conditions is carried out in order to obtain mainly hematite (α-Fe2O3) nanostructures to be used as photocatalysts for photoelectrochemical water splitting applications. Different rotation speeds were studied with the aim of evaluating the obtained nanostructures and determining the most attractive operational conditions. The synthesized nanostructures were characterized by means of Raman spectroscopy, Field Emission Scanning Electron Microscopy, photoelectrochemical water splitting, stability against photocorrosion tests, Mott-Schottky analysis, Electrochemical Impedance Spectroscopy (EIS) and band gap measurements. The results showed that the highest photocurrent densities for photoelectrochemical water splitting were achieved for the nanostructure synthesized at 1000 rpm which corresponds to a nanotubular structure reaching ∼0.130 mA cm−2 at 0.54 V (vs. Ag/AgCl). This is in agreement with the EIS measurements and Mott-Schottky analysis which showed the lowest resistances and the corresponding donor density values, respectively, for the nanostructure anodized at 1000 rpm.