Three-dimensional C@CoO@graphene composite with hollow carbon core and graphene outer layer is fabricated. Benefiting from the coverage of graphene oxide structure, the porous CoO layer can be stabilized and formed between carbon layer and graphene structure. The special nanocomposite exhibits high reversible capacity, good rate capability at high current densities and long-life performance, and retains a high capacity of 861 mAh g−1 at 500 mA g−1 over 700 cycles, making it a promising anode material for Li-ion batteries (LIBs).