Rational fabrication and smart design of multi-component anode materials to achieve desirable reversible capacities and exceptional cyclability are significant for lithium-ion batteries (LIBs). Herein, walnut-like ZnO/Co3O4 porous nanospheres were prepared by a facile solvothermal method, which were then applied as a mechanically stable anode material for LIBs. The rationally designed hybridized electrode brings favorable structural features, particularly ZnO/Co3O4 porous nanospheres with abundant vacant space and enhanced surface area, enhancing lithium/electron transport and relieving volumetric stresses during the cycling process. Moreover, several in situ hybridized anode materials with electrochemical cooperation further overcome the challenge of capacity decay and conductivity deficiency. The as-obtained ZnO/Co3O4 delivered a much better lithium storage performance compared with ZnO, Co3O4, and their physical mix. We believe that the novel design criteria will bring opportunities in exploration and promote the practical application of transition metal oxides.