To illustrate the effect of microwave radiation on the morphologies and electrochemical properties electrode materials, Ni-rich oxide LiNi 0.85 Co 0.05 Mn 0.1 O 2 was identified and prepared from the corresponding precursors synthesized under different reaction conditions. The results suggest that the resultant LiNi 0.85 Co 0.05 Mn 0.1 O 2 morphology controllably depends on its corresponding synthetic method, which will affect its electrochemical property accordingly. The electrode material from microwave-assisted co-precipitation followed by a hydrothermal modification (NCM-WH) possesses a pure α-NaFeO 2 phase and regular spheroidal morphology with a proper size over 10 μm, which exhibits more excellent discharge capacity of ca. 150 mAh g -1 after 200 cycles and better capacity retention of 88.3% than those from microwave-assisted co-precipitation method (NCM-W) or normal co-precipitation method (NCM-N) only. The improved electrochemical properties are confirmed from their ordered phase structure, regular spheroidal morphology and high tap density, which results in lower Li/Ni cation mixing, faster solid-state ion diffusion, higher electrochemical reversibility and better structure stability during the long-tern cycles.