The low-heating solid-state method has been adopted to synthesize LiNi1/3Co1/3Mn1/3O2 materials. The final product, with homogeneous phase and smooth crystals indicated by XRD and SEM results, can be synthesized at 700°C, much lower than the synthesis temperatures of co-precipitation method. The reaction process and microstructure of precursor has been investigated by IR spectrum. By comparative studies with the mixture of CH3COOLi and (Ni, Co, Mn)(C2O4), it is testified that the precursor is homogeneous, rather than a mixture. The decomposition process and the reaction energy have been studied to investigate the reaction mechanism of the precursor when heated at high temperature. The as-synthesized LiNi1/3Co1/3Mn1/3O2 exhibits excellent electrochemical properties, exhibiting initial specific capacity of 167mAhg−1 with stable cyclic performance.