A novel hierarchical network-like Co3O4 are successfully synthesized by hydrothermal method combined with subsequent annealing treatment in air. The evolution process of network-like Co(CO3)0.5(OH)·0.11H2O precursor are characterized by XRD, SEM and FT-IR methods. The as-prepared network-like Co3O4 are tested as an anode material in lithium-ion batteries. The influences of the Co3O4 morphology on the electrochemical performances are investigated. In the specific capability test, the first discharge capacity of 2008mAhg−1 is recorded at current density of 100mAg−1. The excellent electrochemical properties of the Co3O4 electrodes can be attributed to high specific surface area which provides more active area that can react with Li+ ions, leading to outstanding specific capacitance. And the results indicated that the polypyrrole (PPy) as a conductive macromolecule coating on the Co3O4 surface can improve performance of the LIBs obviously.