A novel three-dimensional (3D) porous structured Co3O4 was prepared by electrodeposition combined with thermal-treatment method. The electrochemical properties of as-prepared 3D porous Co3O4 were closely related to its morphology and structure which can be modified by various thermal-treatment temperatures. The 3D porous Co3O4 prepared at 300°C exhibited smaller crystallite size and higher capacity compared to 400°C as well as 500°C. As used in lithium-ion batteries, the porous Co3O4 anodes delivered a high reversible capacity of about 1100mAhg−1 with no obvious capacity fading up to 50 cycles and exhibited higher rate capability compared with Co3O4 foil anodes. The enhanced electrochemical performances of 3D porous Co3O4 anodes are attributed to its unique 3D porous structure which can offer a large materials/electrolyte contact area and accommodate the strain induced by the volume change during cycling.