The surface film, which is formed on graphite negative electrodes during the initial charging, is a key component in lithium secondary batteries. The battery reactions are strongly affected by the nature of the surface film. It is thus very important to understand the physicochemical properties of the surface film. On the other hand, the surface film formation is a very complicated interfacial phenomenon occurring at the graphite/electrolyte interface. In studies on electrode surfaces in lithium secondary batteries, in-situ experimental techniques are very important because the surface film is highly reactive and unstable in the air. In this respect electrochemical atomic force microscopy (ECAFM) is a useful tool for direct visualizing electrode/solution interfaces at which various electrochemical reactions occur under potential control. In the present review, mechanism of surface film formation and its correlation with electrolyte are summarized on the basis of in-situ ECAFM studies for understanding of the nature of the surface film on graphite negative electrodes.