Hierarchical, nanostructured copper oxide spheres were synthesized in a stirred solution of cupric acetate and ammonium hydroxide. Cetyltrimethylammonium bromide (CTAB) was used as a surfactant to modify the surface morphology of CuO spheres. Ordered nano-needle arrays can be formed on the surface of the CuO spheres (instead of disordered nano-leaves) in the presence of CTAB. Each CuO sphere is about 2μm in diameter and possesses a large number of nano-needles that are about 20–40nm in width and more than 300nm in length. The needle-like hierarchical structure can greatly increase the contact area between CuO and electrolyte, which provides more sites for Li+ accommodation, shortens the diffusion length of Li+ and enhances the reactivity of electrode reaction, especially at high rates. After 50 cycles, the reversible capacity of the prepared needle-like CuO can sustain 62.4% and 56.4% of the 2nd cycle at a rate of 0.1C and 1C, respectively.