This study examines the electrochemical reactions occurring at graphite negative electrodes of lithium-ion batteries in a propylene carbonate (PC) electrolyte that contains different concentrations of lithium salts such as, LiClO4, LiPF6 or LiN(SO2C2F5)2. The electrode reactions are significantly affected by the electrolyte concentration. In concentrated solutions, lithium ions are reversibly intercalated within the graphite to form stage 1 lithium–graphite intercalation compounds (Li–GICs), regardless of the lithium salt used. On the other hand, electrolyte decomposition and exfoliation of the graphene layers occur continuously in the low-concentration range. In situ analysis with atomic force microscopy reveals that a thin film (thickness of ∼8nm) forms on the graphite surface in a concentrated solution, e.g., 3.27molkg−1 LiN(SO2C2F5)2/PC, after the first potential cycle between 2.9 and 0V versus Li+/Li. There is no evidence of the co-intercalation of solvent molecules in the concentrated solution.