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Undoped and nickel (Ni)-doped ZnO thin films were spray deposited on glass substrates at 523K using 0.1M of zinc acetate dihydrate and 0.002–0.01M of nickel acetate tetrahydrate precursor solutions and subsequently annealed at 723K. The effect of Ni doping in the structural, morphological, optical and electrical properties of nanostructured ZnO thin film was investigated using X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), UV–vis Spectrophotometer and an Electrometer respectively. XRD patterns confirmed the polycrystalline nature of ZnO thin film with hexagonal wurtzite crystal structure and highly oriented along (002) plane. The crystallite size was found to be increased in the range of 15–31nm as dopant concentration increased. The SEM image revealed the uniformly distributed compact spherical grains and denser in the case of doped ZnO thin films. All the films were highly transparent with average transmittance of 76%. The measured optical band gap was found to be varied from 3.21 to 3.09eV. The influence of Ni doping in the room temperature ethanol sensing characteristics has also been reported.