Layered Li[Ni0.5−x Mn0.5−x Zr2x ]O2 (x =0, 0.025) have been prepared by the mixed hydroxide and molten-salt synthesis method. The individual particles of synthesized materials have a sub-microsize range of 200–500nm, and LiNi0.475Mn0.475Zr0.05O2 has a rougher surface than that of LiNi0.5Mn0.5O2. The Li/Li[Ni0.5−x Mn0.5−x Zr2x ]O2 (x =0, 0.025) electrodes were cycled between 4.5 and 2.0V at a current density of 15mA/g, the discharge capacity of both cells increased during the first ten cycles. The discharge capacity of the Li/LiNi0.475Mn0.475Zr0.05O2 cell increased from 150 to 220mAh/g, which is 50mAh/g larger than that of the Li/LiNi0.5Mn0.5O2 cell. We found that the oxidation of oxygen and the Mn3+ ion concerned this phenomenon from the cyclic voltammetry (CV). Thermal stability of the charged Li[Ni0.5−x Mn0.5−x Zr2x ]O2 (x =0, 0.025) cathode was improved by Zr doping.