A micro-emulsion method has been introduced to synthesize spinel ZnMn2O4. By means of a simple adjustment of the reaction solvent or added surfactant, we successfully gain distinct micro-shapes as porous hexahedron, porous microsphere and porous core-shell microsphere. XRD test results validate the phase purity of resulting ZnMn2O4 materials. Interestingly, the different structural characteristics result in significant disparate electrochemical performances. The porous core-shell microsphere (PCMZ) exerts surprisingly remarkable specific capacity and excellent rate performance. The observed enormous discharge capacity of synthesized PCMZ (similar to 1600 mAh g(-1) for the 100th cycle) is the highest among the ever reported ZnMn2O4-based material. The long cycle performance at high current rate (1208 mAh g(-1) after 250 cycles at 500 mA g(-1)) is also the best. Large amount of experimental results demonstrate that the resulted high specific capacity is mainly assigned to the generation of higher valence Mn during cycling and extra interfacial Li storage caused by its unique architecture. (C) 2017 Elsevier B.V. All rights reserved.