MoO2/Mo2C/C spheres have been synthesized through hydrothermal and calcination processes. MoO2 is well known for its high theoretical capacity of 838 mAh g-1, but undergoes capacity fading during Li+ insertion/extraction processes. Mo2C has high specific conductance (1.02 × 102 S cm-1) that can provide better electronic conductivity. Carbon is popular for its ability to accommodate the volume variation during charge/discharge. By taking advantage of the combination of Mo2C and C, these MoO2/Mo2C/C spheres demonstrate not only high cycling performance, but also good rate capability when they are used as anode materials for lithium ion batteries. After 100 cycles at 100 mA g-1, the discharge capacities of the MoO2/Mo2C/C spheres remain at 800 mAh g-1, suggesting that MoO2/Mo2C/C spheres are promising candidates as anode material for lithium ion batteries.