The deposition of LiCoO2 thin films on a nickel substrate by Electrostatic Spray Deposition (EDS) method was studied. The precursor solution was prepared by dissolving the correct amount of lithium acetate and cobalt acetate into a mixture of 50 mol% ethanol and 50 mol% 2- (2-butoxyethoxy) ethanol. The effect of applied voltage on the jets formed at the tip of nozzle was investigated. The homogeneous deposition of sprayed droplets on the substrate was achieved by spraying in the cone-jet mode. The effect of process parameters such as deposition temperature and nozzle-to-substrate distance on the surface morphology and microstructure of the deposited thin films was examined by scanning electron microscopy (SEM). The deposited LiCoO2 thin films were amorphous or nanocrystalline at the deposition temperature of 523 K. Subsequently, the samples were calcined at 973 K for 2 h in air and were studied using X-ray diffraction (XRD). As the result, the crystal structure of the samples transformed to the desired layered structure. The as-calcined thin films were then used as a cathode active material for lithium-ion battery and their electrochemical properties were investigated. The cyclic performance were found to be affected by the surface morphology of as-prepared thin films.