Composite hollow nanostructure composed by transition metal oxides are promising materials in electrochemistry, catalyst chemistry and material science. In this contribution, necklace-like NiO-CuO heterogeneous composite hollow nanostructures were synthesized by annealing Ni/Cu superlattice nanowires in air. Two kinds of morphologies including CuO nanotube linked core-shell structures and CuO nanotube linked hollow structures were obtained. The structure can be tuned easily by adjusting the relative length of Cu segments in Ni/Cu superlattice nanowires and the annealing temperature. The relative diffusion amount of Cu to Ni segments was proved to be the key factor to influence the annealed sample morphology. The formation mechanism was discussed in detail based on Kirkendal effect and high temperature oxidation of alloy. We demonstrated that hollow structure or core-shell structure is related to whether the oxidation exists only in external sites or co-exists in external and internal sites during annealing.