Although significant advancements in the preparation of metal oxide hollow structures have been achieved, most synthesis routes have some complicated aspects such as requiring a hard-template, multistep procedures or other special reagents. This paper proposes a green and facile bubble-template approach to synthesize and organize Ni-Co hollow microspheres. The entire formation mechanism for the hollow spherical structures, including integration for nucleation, morphological tailoring and an Ostwald ripening process, has been elucidated based on time-dependent observations. The Ni-Co hollow microspheres revealed an excellent cycling stability (730 mA h g(-1) even after 140 cycles at 300 mA g(-1)) and good rate capability when evaluated as an anode material for lithium ion batteries (LIBs). The excellent electrochemical performance can be attributed to the rational design and organization of the hollow structures, which offer a large void space for accommodating volume changes, shorten the diffusion path for Li ions and electron transfer, as well as increase the contact area between the electrodes and electrolyte. Moreover, the synergistic effects of the nickel and cobalt ions with different lithiation potentials allowed the volume change to occur in a stepwise manner. The bubble-template strategy was convenient and very effective for constructing the hollow structures, and if well engineered, it could be extended to the synthesis of other advanced metal oxide anode materials for high energy storage devices and many other applications.