Unique mesoporous Co3O4 octahedra are prepared with the sol-gel method as negative electrode material for lithium-ion batteries. Such an interesting nanostructure that has inherited the combined advantages of anisotropy morphological structure stability and porous feature, which can buffer the volume changes during the electrochemical cycles and shorten the diffusion path of Li+/electron transport, exhibits remarkable electrochemical performance, including high reversible capacity (1195 mAh g−1 at rate of 200mAg−1), good capacity retention (capacity fading of 0.4% per cycle upon 60 cycles), and excellent rate capability (681 mAh g−1 at high rate of 2 A g−1).