LiNi1/3Co1/3Mn1/3O2 is prepared by a rheological phase method. Homogeneous precursor derived from this method is calcined at 800°C for 20h in air, which results in the impressive differences in the morphology properties and electrochemical behaviors of LiNi1/3Co1/3Mn1/3O2 in contrast to that obtained by a solid-state method. The microscopic structural features of LiNi1/3Co1/3Mn1/3O2 are investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD). The electrochemical properties of LiNi1/3Co1/3Mn1/3O2 are carried out by charge–discharge cycling test. All experiments show that the microscopic structural features and the morphology properties are deeply related with the electrochemical performances. The obtained results suggest that the rheological phase method may become an effective route to prepare LiNi1/3Co1/3Mn1/3O2 cathode materials for lithium battery.