Preparation of Cobalt tungstate (CoWO4) thin film by spray pyrolysis with ammonical solution as a precursor is presented. The phase and surface morphology characterizations have been carried out by XRD and SEM analysis. The study of optical absorption spectrum in the wavelength range 350 - 850 nm shows direct as well as indirect optical transitions in the thin film material. The d. c. electrical conductivity measurements in the temperature range 310-500 K indicate semiconducting behavior of the thin film. The thin films deposited on fluorine doped tin oxide (FTO) coated conducting glass substrates were used as a photoanode in photovoltaic electrochemical (PVEC) cell with configuration: CoWO4 vertical bar Ce4+, Ce3+vertical bar Pt; 0.1 M in 0.1 N H2SO4. The PVEC characterization reveals the fill factor and power conversion efficiency to be 0.36 and 0.62%, respectively. The flat band potential is found to be -0.18 V (SCE).