Carbon-coated MoO2 nanocrystallines with uniform particle size and carbon-coating morphology have been fabricated by a green and economical hydrothermal route and carbonization process. Glucose here acts as a multifunctional agent, not only as the reducing species to prepare MoO2, but also as the carbonaceous precursor and coating agent to form the carbon-coated and nanoscale MoO2 crystallines. The electrochemical tests demonstrate that the as-synthesized carbon-coated MoO2 nanocrystallines exhibit high capacity and excellent capacity retention as an anode material for lithium-ion batteries. The specific discharge capacity is as high as 790 mA h g(-1) in the first cycle and 730 mA h g(-1) over 50 cycles. The significant enhancement in the electrochemical Li storage performance is attributed to the synergistic effect of the nanocrystallines structure with small particle size and uniform carbon-coating shell, which reduces the diffusion distance for Li-ion and electron, provides high electric conductivity and relieves the volume effect during the cycling.