Thin CuGaSe2 films were deposited by Vacuum co-evaporation and characterized for their structure, properties and performance as hydrogen-evolving photoelectrodes. The 0.9 mu m thick films were nearly stoichiometric with very slight copper deficiency and showed polycrystalline structure with grain sizes of tens of nanometers. Ail electrode based on such a film was demonstrated operating with outdoor 1-sun photocurrent of up to 13 mA/cm(2). Spectral response data show significant incident-photon-to-current efficiency throughout the visible spectrum, peaking at 63% at 640nm. Photocurrent Output under simulated 1-sun Air Mass 1.5 light was stable over 4 h. Unassisted water-splitting is not possible due to high band edge positions, but operation in tandem Configuration With a Suitable bottom junction is feasible. (C) 2008 Elsevier B.V. All rights reserved.