A procedure for gram-scale synthesis of monodisperse Cu2O nanocubes; by a simple polyol process is demonstrated. The nanocubes are subsequently oxidized to form CuO hollow cubes, spheres, and urchin-like particles, through a sequential dissolution-precipitation process. The CuO urchin-like particles exhibited excellent electrochemical performance and stability, superior to those of hollow structures, for lithium-ion battery anode materials.