ZnO/C hierarchical porous nanorods were synthesized through one-pot wet-chemical reaction followed by thermal calcination. It was found that ZnO/C porous nanorods are composed of numerous nanograins, exhibiting a hierarchical micro/nanostructure. In-situ synchrotron high energy X-ray diffraction study revealed that ZnO/C hierarchical porous nanorods involve a two-step reversible lithiation mechanism during charge/discharge; and part of ZnO and Zn remains at the end of the first discharge and charge process, respectively, leading to a low coulombic efficiency in the initial few cycles. The electrochemical test demonstrated that the reversible capacity and the rate performance of ZnO/C hierarchical porous nanorods anode have been greatly improved by PEDOT-PSS coating, which could maintain a reversible capacity of 623.94mAhg−1 after 1500 cycles at 1C. Its excellent high rate capability and long cycle stability were attributed to the high electronic conductivity of PEDOT-PSS coating layer and the hierarchical structures of ZnO/C porous nanorods.