The applications of ZnO anode material in lithium-ion batteries are limited due to its large volume changes and low electric conductivity in dischargecharge cycles. In the study, the molecular-level design is employed to develop a novel ZnO/porous carbon composite structure. With zinc citrate as the precursor, ZnO/porous carbon microspheres self-assembled by nanosheets are successfully synthesized according to the carbonization method. ZnO particles with the size of 10-30 nm are uniformly dispersed inside porous carbon, which acts as a buffer layer. As the anode material, ZnO/porous carbon microspheres exhibit excellent cycle capacity (557 mAh g À1 at 100 mA g À1 ) and rate performance (304 mAh g À1 at 1 A g À1 ). The as-prepared ZnO/porous carbon microspheres not only guarantee the structural integrity of electrode, but also directly solve the problem of capacity fading. The in situ composite structure may endow ZnO/porous carbon microspheres with wide application potentials in lithium-ion batteries. The study may also pave a new way to design high-performance anode materials for lithium-ion batteries at the molecular scale.