Hierarchical nanostructured NiO (h-NiO) microtubes were prepared by a simple wet-chemical synthesis without the use of template or surfactant, followed by the calcination of alpha-Ni(OH)(2) precursor. The structural characterization of the h-NiO microtubes were performed by scanning microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD), the results of which indicated that the obtained h-NiO microtubes are covered by the nanosheet grown perpendicularly on the tube surface. The unique hierarchical nanostructure of h-NiO microtubes with high surface area and many voids facilitates the electrochemical reaction as well as the short ion and electron transport pathway. Therefore, as anode electrode of Li-ion batteries, the h-NiO microtubes deliver largely enhanced cycle capacity of 770 mAh.g(-1) at a current density of 0.5 C after 200 cycles with high columbic efficiency, compared to the NiO rods. These results suggest that the h-NiO microtubes can be a promising anode material for Li-ion batteries.