Hierarchical MoO2/C microsphere has been successfully prepared via a template-assisted process in the presence of polyethylene glycol followed by thermal annealing. The as-synthesized MoO2/C microsphere with a diameter of about 1.5 mu m had rough surface and good monodispersity. Notably, each microsphere consisted of many nanoparticles with a size of about 20 nm and existed abundant of porous. The MoO2/C microsphere was used as an anode material for lithium ion batteries and its electrical property was also determined in this work. At a current density of 100 mA g(-1), the MoO2/C composite exhibited the discharge specific capacity of 768 mAh g(-1) in the first cycle and 800 mAh g(-1) after 300 cycles. Even at a high current density of 500 mA g(-1), the discharge specific capacity of 565 mAh g(-1) can be maintained after 300 cycles. Such high capacity and excellent cycling stability might be attributed to the hierarchical and porous structure of the MoO2/C, greatly enhancing lithium ions transport and buffering the volume change. Several advantages such as the high electrochemical performance, mild reaction conditions and structural controllability render the hierarchical MoO2/C microsphere as a potential anode material for high performance Li-ion batteries. (C) 2017 Elsevier B.V. All rights reserved.