A novel hybrid of MoO2-ordered mesoporous carbon (MoO2-OMC) was prepared through a two-step solvothermal chemical reaction route. The electrochemical performances of the mesoporous MoO2-OMC hybrids were examined using galvanostatical charge-discharge, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS) techniques. The MoO2-OMC hybrid exhibits significantly improved electrochemical performance of high reversible capacity, high-rate capability, and excellent cycling performance as an anode electrode material for Li ion batteries. It is revealed that the MoO2-OMC hybrid could deliver the first discharge capacity of 1641.8 mA h g(-1) with an initial Coulombic efficiency of 63.6%, and a reversible capacity as high as 1049.1 mA h g(-1) even after 50 cycles at a current density of 100 mA g(-1), much higher than the theoretical capacity of MoO2 (838 mA h g(-1)) and OMC materials. The MoO2-OMC hybrid demonstrates an excellent high rate capability with capacity of ∼600 mA h g(-1) even at a charge current density of 1600 mA g(-1) after 50 cycles, which is approximately 11.1 times higher than that of the OMC (54 mA h g(-1)) materials. The improved rate capability and reversible capacity of the MoO2-OMC hybrid are attributed to a synergistic reaction between the MoO2 nanoparticles and mesoporous OMC matrices. It is noted that the electrochemical performance of the MoO2-OMC hybrid is evidently much better than the previous MoO2-based hybrids.