NiO hollow spheres are prepared by heating the NiCl2/resorcinol-formaldehyde (RF) gel in argon at 700°C for 2h, and subsequently in oxygen at 700°C for 2h. X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) are employed to characterize the structure and morphology of the as-prepared NiO hollow spheres. These hollow spheres have a diameter of about 2μm, which are composed of NiO particles of about 200nm. The electrochemical properties of these NiO hollow spheres are investigated to determine the reversible capacity and cycling performance as anode materials for lithium-ion batteries, and the advantages of their hollow spherical morphology to the electrochemical performance are discussed.