Transparent conducting Li (0-5 wt%) doped NiO thin films with preferential growth along the (111) plane were deposited onto glass substrates by pyrolytic decomposition of nickel nitrate and lithium chloride precursors at 500 °C in air. The effect of Li concentration on the structural, optical and transport properties of NiO thin films was studied by x-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), spectral transmittance, photoluminescence and linear four-probe resistivity. Activation energies as a function of Li concentration were deduced from the temperature dependent resistivity data measured in the range 300-448 K. The figure of merit was deduced by combining the spectral transmittance and sheet resistance values. The variation in properties of NiO thin film due to Li doping are discussed based on the above results. A dye-sensitized solar cell has also been fabricated for the optimized Li doped NiO thin film and the results are presented.