A novel process was proposed for preparing spinel LiMn2O4 with spherical particles from cheap materials of MnSO4, NaOH, NH3•H2O and LiOH. Its successful preparation started with a carefully controlled crystallization of Mn3O4, leading to the spherical shape of its particles and a high tap density. The mixture of Mn3O4 and LiOH was sintered to produce LiMn2O4 with spherical particle size retention. The spherical particles of spinel LiMn2O4 were of excellent fluidity and dispersivity, and had tap density as high as 2.14 g cm-3 and the initial discharge capacity reaching 128 mAh g-1. Its 15th cycle capacity kept to be 125 mAh g-1.