Graphene nanosheets (GNSs) were synthesized by reducing exfoliated graphite oxides. Their structure, surface morphology and lithium storage mechanism were characterized and investigated systematically using X-ray diffraction, atomic force microscopy, scanning electron microscopy, charge-discharge tests, cyclic voltammetry and electrochemical impedance spectroscopy. It was found that the GNSs, which were obtained via chemical synthesis, were primarily less than 10 graphene layers. The GNS electrodes, which were fabricated from the reduced GNSs, exhibited an enhanced reversible lithium storage capacity and good cyclic stability when serving as anodes in lithium-ion batteries. Also, the first-cycle irreversible capacities of the system were relatively high, because of the formation of a solid electrolyte interphase film on the surface of the GNS electrode and the spontaneous stacking of GNSs during the first lithiation. The electrochemical impedance spectroscopy results suggest that the solid electrolyte interphase film on the GNS electrode during first lithiation were primarily formed at potentials between 0.95 and 0.7 V. Also, the symmetry factor of the charge transfer was measured to be 0.446.