The spinel phases of Li1.05RE x Cr y Mn2−x−y O4 (RE=Sc, Ce, Pr, Tb; 0≤ x ≤0.05; 0≤ y ≤0.1) were prepared by a soft chemical method. The structural and electrochemical properties of Li1.05RE x Cr y Mn2−x−y O4 were investigated by X-ray diffraction (XRD), Transmission electron microscopy (TEM) and charge–discharge experiments. Rare earth element-Sc and transition metal-Cr as co-substituents stabilize the spinel framework and improve charge–discharge performance. For Li1.05Sc0.01Cr0.03Mn1.96O4, the capacity of the cell maintained 95% of the initial capacity at the 80th cycle. The rare earth elements of the variable valent metals such as Ce3+/4+, Pr3+/4+, Tb3+/4+ with transition metal Cr3+ as co-substituent do not stable framework of spinel or improve the cycling performance. Cyclic voltammetry (CV) were measured to provide clues for the improved cycling performance of cathode electrodes.