Non-stoichiometric nickel oxide thin films were prepared by pyrolytic decomposition of aerosol droplets of aqueous nickel acetate solution. Conventional un-nebulized spray pyrolysis system was used for the synthesis of thin films. The fine droplets were atomized by employing compressed air as carrier gas and allowed to decompose onto pre-heated Sn doped In2O3 (ITO) coated glass. The preparative parameters such as substrate temperature, solution concentration, distance from spray-nozzle to substrate, pressure of carrier air, etc., were optimized to obtain large area, uniform, thin films. The appropriate substrate temperature was selected after thermo-gravimetric analysis of nickel acetate. The temperature range of 330-420 degrees C was investigated for pyrolysis. Structural studies using X-ray diffraction (XRD) show the formation of cubic NiO. Morphological aspects of the films as-prepared and air annealed films have been studied by employing scanning electron microscopy. The optical absorption studies give direct band gap equal to 3.61 eV. The compositional analysis was carried out from the elemental depth profiles employing Auger electron spectroscopy. These indicate the formation of non-stoichiometric nickel oxide thin films. By studying I-V characteristics in alkaline electrolyte, electrocatalytic activity is tested. (c) 2006 Elsevier B.V. All rights reserved.