Zinc indium selenide (ZnIn2Se4) thin films have been prepared by spraying a mixture of an equimolar aqueous solution of zinc sulphate (ZnSO4), indium trichloride (InCl3), and selenourea (CH4N2Se), onto preheated fluorine-doped tin oxide (FTO)-coated glass substrates at optimized conditions of substrate temperature and a solution concentration. The photoelectrochemical (PEC) cell configuration of n-ZnIn2Se4/1 M (NaOH + Na2S + S)/C has been used for studying the current voltage (I-V), spectral response, and capacitance voltage (C-V) characteristics of the films. The PEC study shows that the ZnIn2Se4 thin films exhibited n-type conductivity. The junction quality factor in dark (n(d)) and light (n(l)), series and shunt resistance (R-s and R-sh), fill factor (FF) and efficiency (eta) for the cell have been estimated. The measured (FF) and eta of the cell are, respectively, found to be 0.435% and 1.47%. (c) 2007 Elsevier B.V. All rights reserved.