LiNi1/3Co1/3Mn1/3O2 has aroused much interest as a new generation of cathode material for Li-ion batteries, due to its great advantages in capacity, stability, low cost and low toxicity, etc. Here we report a novel single-crystalline spherical LiNi1/3Co1/3Mn1/3O2 material that is prepared by a convenient rheological phase reaction route. The X-ray powder diffraction, scanning electron microscopy and transmission electron microscopy indicate that the particles are highly dispersed with spherical morphologies and diameters of about 1–4μm, and more interestingly, they show a perfect single-crystalline nature, which is not usual according to the crystal growth theories and may bring extra benefits to applications. Electrochemical tests show good performance of the material in both the capacity and cycling stability as cathode material in a model cell.