Micro-spherical particle of Ni–Mn–Co alloy was synthesized by powder metallurgy pulverization (PMP) method with Ni, Co and Mn metal as raw materials. Then spherical and dense LiNi1/3Mn1/3Co1/3O2 particle with well-ordered layered structure is obtained by calcining the oxide of Ni–Mn–Co alloy and Li2CO3. The as-prepared material was characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and electrochemical tests. LiNi1/3Mn1/3Co1/3O2 prepared here indicated an initial discharge capacity of 164.4mAhg−1 at 0.1C rate within the voltage range of 2.8–4.3V. The novel method showed high efficiency and environmental friendly for industrialization.