Uniform, hierarchical and porous CoO/C polyhedra were synthesized by impregnating hydrothermally fabricated Co3O4 polyhedra with sugar solution followed by calcination in inert atmosphere. Each CoO/C polyhedron was built up of numerous ordered nanoparticles (around 100nm). As anode material for Li-ion batteries, the CoO/C polyhedra exhibited an initial discharge capacity of 1025mAhg−1, and remained a reversible capacity of 510mAhg−1 after 50 cycles at a current density of 100mAg−1. High Coulombic efficiency over 99% and improved rate capability were achieved for the CoO/C polyhedra. Hierarchical structure and high porosity was benefit to the infiltration of electrolyte and tolerant volume expansion, and hence was responsible for the good electrochemical performance.