Porous hollow LiCoMnO4 microspheres have been prepared and tested as cathode materials for 5 V lithium ion batteries. The microspheres, which combine porous structures in the surface and hollow structures inward, show high capacity, good cyclic reversibility and rate capability as cathode materials for high-voltage Li ion batteries. The LiCoMnO4 microspheres exhibit an initial discharge capacity of 115.5 mAh g−1 at 1 C, maintain a discharge capacity of 91.7 mAh g−1 after 60 cycles with the capacity retention of 79.4%. When cycled at 5 C, the initial capacity is 95.5 mAh g−1, and the capacity retention is 52.6% after 60 cycles. The special porous hollow structure allows for the full contact with the electrolyte, enhances the electrochemical reaction kinetics, and buffers the volume expansion thus maintaining the structural integrity.