Hollow structure NiO nanotubes are produced by a facile fabrication technique from Ni nanowires oxidation through Kirkendall effect. The proposed mechanism for NiO tubular structure formation is derived from the investigation on the oxidation process of Ni nanowires. When these prepared NiO nanotubes are adopted as anode electrode, they demonstrate good capacities. Meanwhile, they also display good rate capability of 93%. Observations have confirmed that the tubular structure of NiO is positive to enhance the contact between NiO and the electrolyte, while also providing void spaces that mitigate volumetric changes in the electrode during lithiation/delithiation processes. These findings suggest that these hollow NiO nanotubes show their potential as efficient and sustainable anode candidate for lithium storage.