MoO2–graphene composite was synthesized via a two-step of hydrothermal-calcination method. The morphology and structure of the products were characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray power diffraction (XRD), and Raman spectroscopy. The content of the graphene in MoO2–graphene composite was examined by thermogravimetric (TG)–differential scanning calorimetry (DSC) analysis. The electrochemical performances of the products were examined by Galvanostatical charge–discharge method, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS). When used as anode material for lithium ion batteries, the MoO2–graphene composite shows an enhanced cyclic performance and lithium storage property. The first discharge capacity of the composite can reach 674.4mAhg−1 with a reversible capacity of 429.9mAhg−1. Significantly, the composite can also deliver a reversible capacity of as high as1009.9mAhg−1 after 60 charge/discharge cycles.