Solid sphere spinel LiMn2O4 materials are synthesized from porous spherical Mn3O4 particles with LiOH·H2O via a high temperature solid-phase reaction. Porous spherical Mn3O4 particles, composed of aggregated crystallites, can be obtained from as-prepared spherical β-MnOOH. The solid sphere spinel LiMn2O4 particles have a high tap-density of 2.67 g·cm−3 and are well-distributed with sizes ranging from 7-9μm. The as-prepared β-MnOOH, Mn3O4 and LiMn2O4 are characterized by X-ray diffraction and scanning electron microscopy. As cathode materials, solid sphere spinel LiMn2O4, exhibits excellent cycling performance and rate capability for lithium-ion batteries. The initial discharge capacities are 127.1, 118.1, 106.3 and 87 mAh·g−1 at 0.2, 1, 5 and 10C, respectively. At 5C the discharge capacity retention rate can be maintained at 95% after 200 cycles. Cyclic voltammetry and electrochemical impedance spectroscopy confirm the excellent electrochemical performances of the synthesized solid sphere spinel LiMn2O4 materials.