High valency spherical Ni1/3Co1/3Mn1/3OOH and low valency spherical Ni1/3Co1/3Mn1/3(OH)2 precursor powders were synthesized respectively by co-precipitation method and oxidation method at different conditions. And then spherical Li(Ni1/3Co1/3Mn1/3)O2 powders were prepared at different temperature by their precursors, which were sintered with LiOH·H2O. XPS studies indicated that the predominant oxidation states of Ni, Co and Mn in spherical precursor Ni1/3Co1/3Mn1/3OOH were 2+, 3+ and 4+, furthermore, the spherical Li(Ni1/3Co1/3Mn1/3)O2 powders with a well-ordered layered α-NaFeO2 structure and small amount of cation mixing can be synthesized at low temperature by Ni1/3Co1/3Mn1/3OOH, which indicated that the activity of spherical Ni1/3Co1/3Mn1/3OOH is higher than that of spherical Ni1/3Co1/3Mn1/3(OH)2. Charge and discharge capacity showed that the synthesized spherical cathodes by Ni1/3Co1/3Mn1/3OOH delivered higher discharge capacity and better cycling properties