In this study, a metastable form of vanadium dioxide, denoted as VO2(B), has been successfully synthesized under solvothermal condition. However, the as-received VO2(B) suffers from fast capacity fading and poor high-rate performance. In order to overcome these problems, the as-received VO2(B) is solvothermally treated with reduced graphene oxide (rGO) to produce VO2(B)/rGO composite. As a result, the resulting electric conductivity of the VO2(B)/rGO composite is improved to ∼10−4 cm S−1 (from ∼10−7 S cm−1 for the as-received VO2(B)). Electrochemical data of the VO2(B)/rGO composite, tested in both Li and Na cells, shows markedly enhanced electrochemical performance compared to bare VO2(B). The effect of electro-conducting rGO is more evident at high rates.