We report on the strategy of Cu doping inducing the nanosize effect of CoO and their application as anode for lithium ion batteries. With an increase of Cu-doped amount, the structures and morphologies of CoO have special changes. The 0.05 mol Cu-doped CoO shows straw-like bundle structure assembled by nanorods, and the nanorods consist of ultra small nanoparticles (about 6–8 nm). Meanwhile, it shows an excellent rates performance and cycle life. The capacity of 800 mA h g−1 is obtained at 0.5 C after 80 cycles. The highest discharge capacity is 580 mA h g−1 at 10 C and the discharge capacities are relatively stable for 1000 cycles as an anode for Li-ion battery. Therefore, the controllable Cu-doped CoO composite could be deemed to be a potential candidate as an anode material.