The layered Li[Ni1/3Co1/3Mn1/3]O2 materials were synthesized by a spray pyrolysis method using citric acid as a polymeric agent. The Li[Ni1/3Co1/3Mn1/3]O2 powders were characterized by means of X-ray diffraction (XRD), charge/discharge cycling, cyclic voltammetry, and high-resolution transmission electron microscopy (TEM). The discharge capacity increases linearly with the increase of the upper cut-off voltage limit. TEM analysis showed that particles in the as-prepared powder possessed a polycrystalline structure. During cycling, the particle structure is mostly preserved although some surface grains on the polycrystalline particle became separated and transformed to the spinel phase.