The nickel foam-supported porous NiO–Ni nanocomposite synthesized by electrostatic spray deposition (ESD) technique was investigated as anodes for lithium ion batteries. This anode was demonstrated to exhibit improved cycle performance as well as good rate capability. Ni particles in the composites provide a highly conductive medium for electron transfer during the conversion reaction of NiO with Li+ and facilitate a more complete decomposition of Li2O during charge with increased reversibility of conversion reaction. Moreover, the obtained porous structure is benefical to buffering the volume expansion/constriction during the cycling.