Hollow spheres consisting of porous CNT/CuO nanocomposite networks were prepared by aerosol process and their enhanced anodic properties for lithium-ion battery were investigated. Hollow spheres of CNT/CuO nanocomposites showed a 3D network wherein the length of the electron path was quite short compared with the agglomerated CNT/CuO nanocomposites. From electrochemical measurements, CuO itself shows poor discharge capacity and cycling performance due to its low electronic conductivity. In the CNT/CuO nanocomposite, enhanced discharge capacity was observed and showed similar values regardless of the morphology. With the addition of CNTs to CuO, CNTs can form a network that acts as an electron path-way in the insulating CuO matrix, leading to increased electrical conductivity. The morphology of nanocomposite affected cycle stability. Hollow spheres of CNT/CuO nanocomposite showed better cycle stability than that of agglomerated CNT/CuO nanocomposite. The hollow sphere of a CNT/CuO nanocomposite comprising a 3D network of CNTs can be applied as a high capacity anode material in Li-ion batteries.