LiMn2O4-coated LiCoO2 film was synthesized by the ESD technique. The bulk structure and its electrochemical property were studied by X-ray diffraction (XRD) and cyclic voltammetry (CV) and the surface structure were characterized using soft XAS at the O K-edge and the Mn L-edge. The bulk structure and the electrochemical property of the LiMn2O4-coated LiCoO2 film do not show substantial difference compared to the bare LiCoO2 film. The thermal stability of LiCoO2 film is improved by LiMn2O4 coating on the surface of the LiCoO2 film. The Mn L-edge and O K-edge results suggest that the structure at the surface of LiMn2O4-coated LiCoO2 film is a spinel LiCo x Mn2−x O4.