Nanostructured CuO anode materials with controllable morphologies have been successfully synthesized via a facile and environmentally friendly approach in the absence of any toxic surfactants or templates. In particular, leaf-like CuO, oatmeal-like CuO, and hollow-spherical CuO were obtained by changing the ligand agents. The structures and electrochemical performance of these as-prepared CuO were fully characterized by various techniques, and the properties were found to be strongly dependent on morphology. As anode materials for lithium-ion batteries, the leaf-like CuO and oatmeal-like CuO electrodes exhibit relatively high reversible capacities, whereas hollow-spherical CuO shows enhanced reversible capacity after initial degradation. Furthermore, an excellent high rate capability was obtained for the leaf-like CuO and hollow-spherical CuO electrodes. These results may provide valuable insights for the development of nanostructured anodes for next-generation high-performance lithium-ion batteries.