Controlled Mn3O4 hollow polyhedron with average size of 1 mu m was successfully synthetized via one-step hydrothermal method, followed by coated with carbon layer on the surface of the polyhedron using dopamine as carbon source to form the hollow core-shell structured Mn3O4@C composites. The unique morphology and strong structure effectively enhanced the cycling stability of electrode materials. The electrochemical results show that the as-prepared Mn3O4@C composite exhibits outstanding electrochemical lithium storage properties with high initial discharge capacity of 2057.1 mAhg(-1) and a superior cycling performance that could maintain about 885.5 mAhg(-1) after 200 cycles at a 100 mAg(-1) current density. These promising results demonstrate that the Mn3O4@C composite could be promising LIBs anode materials.