The hybrid systems composed by [FeFe]-hydrogenase anchored to the surface of three distinct types of TiO2 (anatase) have been investigated using Electron Paramagnetic Resonance (EPR) spectroscopy in dark and under illumination. The three supports were bare TiO2, nitrogen doped TiO2 (N-TiO2) and a sub-stoichiometric form of the same oxide (TiO2-x) exhibiting blue color. EPR spectroscopy has shown that the electrons photo generated by irradiation of the supports are stabilised by the solid forming Ti3+ paramagnetic ions while, in the case of the hybrid systems electrons are scavenged by the anchored protein becoming available for H+ reduction. The ability of the three hybrid systems in hydrogen production under solar light illumination has been compared. The formation of H-2 is higher for the system containing N-TiO2 (yellow) with respect to that based on the bare oxide (white) indicating that the visible light absorbed, due to the presence of N states, is actually exploited for hydrogen production. The system containing reduced blue TiO2, in spite of its deep coloration, is less active suggesting that a specific type of visible light absorption is needed to produce photoexcited electrons capable to interact with the anchored protein. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.