Lithium nickel manganate is recognized as a type of promising cathode material for lithium-ion battery, due to its advantages such as high voltage, high power density, and relative lower cost. In this paper, a series of LiNi x Mn2 − x O4 cathode materials with various molar ratio of Ni/Mn have been prepared with a co-precipitation method, followed by a solid state reaction, and the effect of the molar ratio of Ni/Mn on the structure and properties of materials are intensively investigated by means of X-ray diffraction (XRD), Fourier transform infrared spectrometer (FTIR), scanning electron microscopy (SEM), and performance measurements, etc. It is revealed that all the samples with x from 0 to 0.5 have well-defined spinel structure and fit well to Fd-3 m space group. With the increase of the molar ratio of Ni/Mn, the diffraction peaks shift to higher angle slightly and the lattice parameter decreases gradually by the XRD results. Furthermore, it is found that the capacity at the 4.0 V plateau decreases while the capacity at 4.7 V plateau increases with the increase of the ratio of Ni/Mn, and the total discharge capacity shows growth trend with the increase of Ni content. It is important that all the samples with various molar ratio of Ni/Mn exhibit good cyclic stability. Based on the experimental results, we suggest that the Ni may incorporate into the lattice of LiMn2O4 substituting of Mn. The plateau at 4.7 V is related to the Ni ions and the plateau at 4.0 V is related to the Mn ions in the materials.