Pt film was prepared by electrospray deposition technique from solution prepared in different solvents (water, ethanol, and the mixture of both solvents), which was characterized by different analytical techniques. In the scanning electron microscopic images, the surface morphology of the film prepared from water solvent was porous, which was slowly changed into morphology of scattered spherical grains on highly compact and uniform surface with ethanol concentration. From the XPS spectra it was observed that the film prepared from water solvent was in hydroxide form, whereas the film prepared from ethanol was in pure Pt form. The film prepared from mixture of both the solvent was observed in mixed phases and its purity was found to be increased with ethanol concentration. The linear sweep plot was used for catalytic activity study of the film for hydrogen evolution reaction (HER) and PV assisted water electrolysis system for volumetric hydrogen production measurement. From the linear sweep plot low overpotential value concludes high catalytically active for HER, was observed in the film prepared from ethanol solvent, which (overpotential value) was found to increase in a film with increase in water solvent. The volumetric hydrogen evolution study also showed similar trend as observed in linear sweep plot. (C) 2012 Elsevier B.V. All rights reserved.