LiCoO2 thin film cathodes were prepared by RF magnetron sputtering and post-annealing. The surface morphological change of the LiCoO2 thin film was in-situ measured by hot stage SEM with increasing temperature. The effects of sputtering gas pressure and post-annealing at low temperature (400 ℃) were investigated by XRD, AFM, ICP-AES and RBS. The electrochemical characteristics of LiCoO2 thin films were changed with variation of sputtering gas pressure. A difference of micro-structural evolution after post-annealing was observed, which related to the thin film properties. The electrochemical analysis revealed that the optimal sputtering gas pressure with the low temperature annealing step increases cell capacity and rate capability.