Photoelectrochemical Impedance Spectroscopy (PEIS) has been used to characterize the kinetics of electron transfer and recombination taking place during oxygen evolution at illuminated polycrystalline α-Fe(2)O(3) electrodes prepared by aerosol-assisted chemical vapour deposition from a ferrocene precursor. The PEIS results were analysed using a phenomenological approach since the mechanism of the oxygen evolution reaction is not known a priori. The results indicate that the photocurrent onset potential is strongly affected by Fermi level pinning since the rate constant for surface recombination is almost constant in this potential region. The phenomenological rate constant for electron transfer was found to increase with potential, suggesting that the potential drop in the Helmholtz layer influences the activation energy for the oxygen evolution process. The PEIS analysis also shows that the limiting factor determining the performance of the α-Fe(2)O(3) photoanode is electron-hole recombination in the bulk of the oxide.