Polycrystalline n-CdSe thin films were prepared by electrodeposition at controlled current density on conducting substrates. The optical characteristics were determined through transmittance spectra. Scanning electron microscopy and atomic force microscopy were employed to study the morphology of the semiconductor (SC) surfaces. Chemical composition of the SC film was established by EDAX analysis. The n-CdSe/electrolyte junctions in water and non-aqueous solvents like acetonitrile (ACN), dimethyl formamide (DMF), dimethyl sulphoxide (DMSO) and propylene carbonate (PC) were characterized by Mott-Schottky analysis using frequency response analyzer. The stability of CdSe layers in water and in non-aqueous solvents was determined through anodic polarization studies. Anodic stripping voltammetry was employed to find out the dissoluted Cd2+ in solution. Photovoltage was measured under illuminated conditions using ferrocene-ferricenium couple in aqueous and non-aqueous solvents throughout the temperature range of 20-70degreesC. The results are indicative of the potential use of the electrodeposited n-CdSe in selected non-aqueous medium for solar energy conversion by photoelectrochemical (PEC) devices. (C) 2004 Elsevier B.V. All rights reserved.