Photoelectrolysis of water by solar radiation to produce hydrogen is achieved using semiconducting thin film electrodes. The cell comprises (a) an anodic electrode comprising at least one thin n-type semiconducting layer which has a bandgap ranging from about 0.5 to 4.0 eV and which is disposed on a supporting conductive substrate; (b) a cathodic counter-electrode comprising at least one thin p-type semiconducting layer which has a bandgap ranging from about 0.5 to 4.0 eV and which is supported on a supporting conductive substrate, the p-type layer adjacent the n-type layer being such that incident solar radiation impinges substantially simultaneously on both the n- and p-type electrodes; (c) means for retaining an electrolyte in contact with the exposed surfaces of the n- and p-type semiconducting electrodes; (d) external bias means between the electrode and the counter-electrode for biasing the cell with from 0 to about 1 V; and (e) means for collecting hydrogen and any oxidation products produced.
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