A facile topochemical route has been developed to synthesize porous LiMn2O4 spheres by using molten LiOH and porous Mn2O3 spheres as a template. The presence of pores with the average size of about 45 nm throughout the whole LiMn2O4 microspheres was confirmed by transmission electron microscope (TEM) and N-2 adsorption-desorption measurements. When applied as cathode materials for rechargeable lithium-ion batteries, the porous sphere LiMn2O4 revealed stable high-rate capability. The discharge capacity is 83 mAh g(-1) at 20 C rate, and it shows a good capacity retention after cycling at constantly changing discharge rate. Taking the excellent electrochemical performance and facile synthesis into consideration, the presented porous LiMn2O4 spheres could be a competitive candidate cathode material for high-performance lithium-ion batteries. (C) 2012 Elsevier B.V. All rights reserved.