Sheaf-like CuO nanostructures have been synthesized by a simple hydrothermal process conducted at 120°C for 24h. The crystalline structure and morphology of the as-synthesized powder have been characterized by using X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FESEM) and transmission electron microscope (TEM). And the growth process of the sheaf-like nanostructures was also clarified. The electrochemical performance as anode material for lithium-ion batteries was further evaluated by charge–discharge measurements. It was found that the sheaf-like CuO electrode can exhibit a high initial discharge capacity of 965mAh/g. After 41 cycles, the electrode can deliver a capacity of 580mAh/g. And a high rate capability was also obtained.