The first electrochemical lithium insertion was characterized for several graphite materials with high degree of crystallinity, different particle size distributions and surface morphologies in an ethylene carbonate (EC)/propylene carbonate (PC) electrolyte. For coarser graphite materials and graphites with a low superficial defect concentration, an irreversible process was observed which correlated with the electrochemical exfoliation of graphite. Different natural and synthetic graphites with similar particle size distribution and active surface area showed differences in the passivation behavior during the first electrochemical reduction. The fraction of graphite particles exfoliating during the first galvanostatic lithium insertion linearly increased with length of the irreversible plateau, which concomitantly moved to more positive potentials. This behavior can be rationalized when considering, besides the surface structure, local overpotentials for the solid electrolyte interphase formation process, and especially the overpotential distribution through the graphite electrode. These overpotentials cause a distribution of the local current density attributed to the passivation process. Optimizing the particle contacts in the electrode by applying mechanical pressure or by selecting the proper binder decreased the overpotentials and suppressed the graphite exfoliation in the EC/PC electrolyte. Therefore, both graphite surface structure and electrode engineering aspects have to be considered for successful passivation against exfoliation.