A facile two-step strategy involving a polyol method and subsequent thermal annealing treatment is successfully developed for the large-scale preparation of ZnCo2O4 various hierarchical micro/nanostructures (twin mcrospheres and microcubes) without surfactant assistance. To the best of our knowledge, this is the first report on the synthesis of ZnCo2O4 mesoporous twin microspheres and microcubes. More significantly, based on the effect of the reaction time on the morphology evolution of the precursor, a brand-new crystal growth mechanism, multistep splitting then in situ dissolution recrystallization accompanied by morphology and phase change, is first proposed to understand the formation of the 3D twin microshperes, providing new research opportunity for investigating the formation of novel micro/nanostructures. When evaluated as anode materials for lithium-ion batteries (LIBs), ZnCo2O4 hierarchical microstructures exhibit superior capacity retention, excellent cycling stability at the 5 A g-1 rate for 2000 cycles. Surprisingly, the ZnCo2O4 twin microspheres show an exceptionally high rate capability up to the 10 A g-1 rate. It should be noted that such super-high rate performance and cycling stability at such high charge/discharge rates are significantly higher than most work previously reported on ZnCo2O4 micro/nanostructures and ZnCo2O4-based heterostructures. The ZnCo2O4 3D hierarchical micro/nanostructures demonstrate the great potential as negative electrode materials for high-performance LIBs.