Cobalt tetroxide composite carbon materials (Co3O4/MWCNTs) are used as anode electrode materials for lithium-ion batteries and have excellent electrochemical performance. A simple method to synthesize Co3O4 hollow microspheres with a hollow spherical MOF precursoras a self-sacrificial template formed by trimesic acid and cobalt nitrate hexahydrate was proposed. Co3O4/MWCNTs as a anode electrode material for lithium-ion batteries, exhibits excellent rate performance and long cycle performance. The Co3O4/MWCNTs electrode showed a high specific capacity of 710 mAh·g−1 after 100 cycles at 0.1A·g−1, and an excellent capability of 633.4 mAh·g−1 after 200 cycles at 0.5A·g−1.