When lithium is intercalated into graphite in ethylene carbonate (EC) containing electrolytes, solvent co-intercalation leading to the exfoliation of the graphite structure could occur. The exfoliation can be suppressed if an efficient solid electrolyte interphase (SEI, a passivation layer) is formed. Here we study the role played by the active surface area (ASA) of graphite materials during their first electrochemical reduction. ASA (related to the presence of defects at the carbon surface) appears as a critical graphite surface parameter influencing the surface passivation mechanism and the graphite exfoliation. The ASA of TIMREX® SLX50 synthetic graphite was modified by thermal treatment in argon and air. The electrochemical performance was characterized in 1M LiPF6, EC:DMC electrolyte and post mortem analyses were performed by SEM imaging. It turned out that a decrease of the graphite ASA, i.e., an increase of the graphite structural order, hinders the formation of the passivation layer and favors the exfoliation process. In contrast, the exfoliation of the same graphite can be suppressed if its ASA is increased for example by air treatment. The ASA of the graphite kinetically controls the formation of an efficient SEI film and accordingly the irreversible charge loss is much lower in the case of graphite with a high ASA value.