Deposition of composite thin film of polyaniline/TiO₂ (PAni/TiO₂) has been carried out by a combined process of magnetron sputtering and plasma polymerization at a pressure of 5 × 10⁻² Torr using titanium as a target material for sputtering, aniline as monomer, oxygen as reactive gas and argon as carrier gas/ion source for sputtering. The deposition has been achieved using direct current (dc) discharge power of 35 W for sputtering and radio frequency (rf) power of 8–12 W at substrate bias values in the ranges of −80 to −100 V for polymerization. The composition of the film has been studied using infrared spectroscopy, Raman spectroscopy as well as X-ray photoelectron spectroscopy. The morphology of the film has been characterized with the help of a transmission electron microscopy and atomic force microscopy. The ultraviolet (UV) photo-stability of the composite film has been studied by exposing the film deposited on silicon substrate for different reaction times up to 1 h under UV radiation at wave length range of 280–400 nm with an intensity of 0.4 mW/cm². An organic/inorganic nanocomposite film based photovoltaic device has been developed. The device has an aluminum/composite/indium tin oxide sandwiched structure that shows strong photoresponse in ultraviolet region and hence the device has potential for application as an UV detector.