Polycrystalline cadmium selenide (CdSe) thin films have been prepared by spraying a mixture of an equimolar aqueous solutions of cadmium chloride and selenourea on preheated fluorine doped tin oxide (FTO) coated glass substrates at different substrate temperatures. The cell configuration n-CdSe/1 M (NaOH + Na(2)S + S)/C is used for studying the capacitance voltage (C-V) characteristics in dark, current voltage (I-V) characteristics in dark and under illumination, photovoltaic power output and spectral response characteristics of the as deposited films. Photoelectrochemical study shows that as deposited CdSe thin films exhibits n-type of conductivity. The spectral response characteristics of the films at room temperature show a prominent sharp peak at 725 nm. The measured values of efficiency (eta) and fill factor (FF) are found to be 0.50% and 0.44 respectively for film deposited at 300 degrees C. Electrochemical impedance spectroscopy studies show that the CdSe film deposited at 300 degrees C shows better performance in PEC cell. (C) 2010 Elsevier Ltd. All rights reserved.