Hierarchical mesoporous LiNi 1/3 Co 1/3 Mn 1/3 O 2 spheres have been synthesized by urea-assisted solvothermal method with adding Triton X-100. The structure and morphology of the as-prepared materials were analyzed by X-ray diffraction and electron microscope. The results show that the as-prepared samples can be indexed as hexagonal layered structure with hierarchical architecture, and the possible formation mechanism is speculated. When evaluated as cathode material, the hierarchical mesoporous LiNi 1/3 Co 1/3 Mn 1/3 O 2 spheres show good electrochemical properties with high initial discharge capacity of 129.9 mAh g −1 , and remain the discharge capacity of 95.5 mAh g −1 after 160 cycles at 10C. The excellent electrochemical performance of the as-prepared sample can be attributed to its stable hierarchical mesoporous framework in conjunction with large specific surface, low cation mixing and small particle size. They not only provide a large number of reaction sites for surface or interface reaction, but also shorten the diffusion length of Li + ions. Meanwhile, the mesoporous spheres composed of nanoparticles can contribute to high rate ability and buffer volume changes during charge/discharge process.