The layered Li[Ni1/3Co1/3Mn1/3]O2 powder with good crystalline and spherical shape was prepared by hydroxide co-precipitation method. The effects of pH value, NH4OH amount, calcination temperature and extra Li amount on the morphology, structure and electrochemical properties of the cathode material were investigated in detail. SEM results indicate that pH value affected both the morphology and the property of the cathode material, and the highest discharge capacity in the first cycle of 163mAhg−1 (2.8–4.3V) was obtained at pH value was 12. On the contrary, the NH4OH amount, which was used as a chelating agent, only affected the particle size distribution of the material. The calcination temperatures caused great difference in the structure and property of layered Li[Ni1/3Co1/3Mn1/3]O2, and the best electrochemical properties were obtained at the calcination temperature of 800°C. Extra Li amount not only caused difference in the material structure, but also affected their electrochemical properties. With increasing Li amount, the lattice parameters (a and c) increased monotonously, and the highest first cycle coulombic efficiency (the ratio of discharge capacity to charge capacity in the first cycle) was obtained with the Li/M of 1.10. Therefore, the optimum synthetic conditions for the hydroxide co-precipitation reaction were: pH value was 12, NH4OH amount was 0.36molL−1, calcination temperature was 800°C and the Li/M molar ratio was 1.10.