Li[Ni1/3Co1/3Mn1/3]O2 powders were synthesized from co-precipitated spherical metal hydroxide, (Ni1/3Co1/3Mn1/3)(OH)2. The preparation of metal hydroxide was significantly dependent on synthetic conditions, such as pH, amount of chelating agent, stirring speed, etc. The optimized condition resulted in (Ni1/3Co1/3Mn1/3)(OH)2, of which the particle size distribution was uniform and the particle shape was spherical, as observed by scanning electron microscopy. Calcination of the uniform metal hydroxide with LiOH at higher temperature led to a well-ordered layer-structured Li[Ni1/3Co1/3Mn1/3]O2, as confirmed by Rietveld refinement of X-ray diffraction pattern. Due to the homogeneity of the metal hydroxide, (Ni1/3Co1/3Mn1/3)(OH)2, the final product, Li[Ni1/3Co1/3Mn1/3]O2, was also significantly uniform, i.e., the average particle size was of about 10μm in diameter and the distribution was relatively narrow. As a result, the corresponding tap-density was also high approximately 2.39gcm−3, of which the value is comparable to that of commercialized LiCoO2. In the voltage range of 2.8–4.3, 2.8–4.4, and 2.8–4.5V, the discharge capacities of Li[Ni1/3Co1/3Mn1/3]O2 electrode were 159, 168, and 177mAhg−1, respectively. For elevated temperature operation (55°C), the resulted capacity was of about 168mAhg−1 with an excellent cyclability.