The electrochemical intercalation of lithium and sodium into graphite was carried out using a liquid electrolyte containing ethylene carbonate (EC) as solvent and MClO4 or MBF4 (M = Li, Na) as salts. The first intercalation of alkali metals into graphite is accompanied with irreversible reactions attributed to the reduction of the electrolyte. These reactions contribute to the development of a passivating layer, formed on graphite surface prior to intercalation. This layer is impervious to solvent molecules but allows alkali ions to diffuse through its bulk. The surface chemistry of the electrodes was characterized using transmission electron microscopy (image, selected area electron diffraction) as well as EELS. The effect of the nature of the alkali salts on the properties of the passivating layer is studied.