Owing to its environmental-benignity, low-cost and abundance, spinel LiMn2O4 has long been considered as a promising cathode material for lithium-ion batteries (LIBs). However, the low electronic conductivity, small lithium diffusion coefficient and poor capacity retention hindered its further development and application. Herein, we report the synthesis of multi-shelled LiMn2O4 hollow microspheres through a hard template method, with the composition, shell number, shell thickness and porosity accurately controlled. Benefitting from the structural superiorities of multi-shelled hollow structures, the triple-shelled LiMn2O4 hollow microsphere exhibits a better cycling stability than all the reported results based on un-coated or un-doped LiMn2O4 (the capacity fading rate is 0.10% per cycle).