Multi-layer thin films of LiMn2O4/SrRuO3 have been epitaxially grown on SrTiO3 (111) substrates using a pulsed laser deposition method. The multi-layer electrodes show excellent electrochemical properties due to introduction of an electronic conducting buffer layer between the lithium cathode film and semiconducting substrate. Moreover, the electrochemical characteristics of the lithium cathode materials are strongly dependent on the electronic contact. Thus, the epitaxially grown electrodes can be used as ideal crystalline models to obtain information about the lattice plane, surface roughness, and thickness of electrodes. This information can be used to elucidate the reaction mechanisms of lithium batteries.