It is well known that a protective film is formed on the graphite negative electrode in ethylene carbonate (EC) electrolyte solution. This film is lithium-ion conductive and protects the decomposition of the electrolyte solution. In the present paper, the electrode/electrolyte interfaces in lithium-ion rechargeable batteries were characterized by three-dimensional complex impedance plots, whose axes are real, imaginary parts and time. The film resistance R sei and charge transfer resistance R ct were determined for negative electrodes in EC/ethyl methyl carbonate (EMC) electrolyte solution, and the formation mechanisms of the interfacial film were discussed. Furthermore, the contributions of vinylene carbonate and ethylene sulfite, which are added into the electrolyte solution for the film formation, were investigated.