LiCoO2 thin-film cathode was deposited on Pt-coated alumina substrate by the electrostatic spray deposition method. The average film weight of LiCoO2 increased linearly with the deposition time. Electrochemical characterization was carried out by cyclic voltammetry and charge/discharge tests. These tests revealed that single phase HT-LiCoO2 films could be obtained by the ESD method at temperature as low as 600°C and the LiCoO2 film deposited by the ESD method showed very stable cycling characteristics. The crystallinity of the LiCoO2 layers increased with increasing annealing temperature. XANES results showed that the LiCoO2 film deposited by the ESD method does not show any changes of the local geometry and electronic structure around Co atoms after electrochemical cycling.