Polycrystalline, (111) textured single CdSe and binary CdSe/ZnSe thin films were prepared by electrodeposition and used as active electrodes in regenerative, liquid junction solar cells with aqueous sulphide-polysulphide or ferro-ferricyanide redox electrolytes. The influence of ZnSe on the photoelectrochemical properties of CdSe was investigated. Microchemical characterization of the cell ingredients was made by X-ray diffraction, scanning microscopy imaging and atomic absorption spectrophotometry. The semiconductor electrodes could behave as rectifying diodes within certain conditions, though cell operation was inevitably associated to chemical changes of the electrodes. Aspects of the corrosion effects are discussed and the stabilization of particular cells is demonstrated. (c) 2006 Elsevier B.V. All rights reserved.