Cadmium indium selenide (n-CdIn 2Se4) thin films have been synthesized by spraying the mixture of an equimolar solutions of cadmium chloride [CdCl2], indium trichloride [InCl3] and selenourea [(NH2)2CSe] in aqueous media onto preheated fluorine doped tin oxide (FTO) coated glass substrates at optimized parameters of substrate temperature and solution concentration. The photoelectrochemical (PEC) cell configuration of n-CdIn2Se/(l MNaOH + 1 MNa2S + 1 M S)/C has been used for investigating the current-voltage (I-V) characteristics under dark and white light illumination, photovoltaic output, spectral response, photovoltaic rise and decay characteristics. The PEC study reveals the thin film of CdIn2Se4 exhibits 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 (η) for the cell have been estimated. The observed efficiency and FF of PEC solar cell is found to be 1.95 and 0.37% respectively. Mott-Schottky plot shows the flat-band potential (V fb) of n-CdIn2Se4/(l M NaOH + 1 M Na2S + 1 M S)/C cell to be-0.655 V/SCE. © 2010 Allerton Press, Inc.