Topographic and frictional changes on the surface of a highly oriented pyrolytic graphite electrode in 1 M LiClO4 ethylene carbonate/ethylmethyl carbonate (1:1) electrolyte were examined during charge and discharge by in situ electrochemical atomic force microscopy and friction force microscopy simultaneously in real-time. Solid electrolyte interphase film formation commenced at approximately 2 V vs. Li/Li+ and stable film formation with an island-like morphology was observed below approximately 0.9 V vs. Li/Li+. Further experiments on a KS-44 graphite/polyvinylidene difluoride binder composite electrode showed similar phenomena.