The approach of using hydrogen for an energy store to offset seasonal variations in solar energy is one very much at the periphery of current renewable energy system design. Nonetheless, its inherent advantages for long term storage in stand alone power systems warrant further detailed investigation. This paper provides a comparative overview of the very disparate technologies within two generic approaches to achieving this goal. These are: photovoltaic (PV) powered electrolysis of water and direct photoelectrolytic (PE) generation of hydrogen from water. Comparison of these is difficult, however, the paper compares devices of similar material system and structure within each generic scheme. PV/electrolysis is the more mature technology but there is still a wide range of potential 'solar to hydrogen' efficiencies. A figure of about 9% is estimated for comparison, with justification given. The comparative figure for PE is more difficult to judge because of even more disparate approaches to specific problems of sufficient photovoltage and stability, but an approximate comparative figure of 5% is estimated. Thus making PV/electrolysis more appropriate at present. Nonetheless, inherent advantages of simplicity of system design and potential robustness mean that PE may become more appropriate as the technology develops. (c) 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.