Partial substitution of Mn in lithium manganese oxide spinel materials by Cu and Ni greatly affects the electrochemistry and the cycle life characteristics of the cathode. Substitution with either metal or a combination of both metals in the spinel lattice structure reduces the 3.9–4.2V potential plateaus associated with the conversion of Mn3+ to Mn4+. Higher potential plateau associated with oxidation of the substituted transition elements is also observed. These substituents also significantly alter the onset of Jahn–Teller distortions in the 3V potential plateau. Synchrotron based in situ X-ray absorption (XAS) was used to determine the exact nature of the oxidation state changes in order to explain the overall observed capacities at different potential plateaus. The studies on LiCu0.5Mn1.5O4 show single phase behavior in the 4–5V potential region with a good cycle life. Lower cycle life characteristic observed in cycling LiNi0.5Mn1.5O4 and LiNi0.25Cu0.25Mn1.5O4 versus Li metal are ascribed to coexistence of several phases in this potential region. However, LiCu0.5Mn1.5O4 shows onset of Jahn–Teller distortions in the 3V potential plateau, in contrast to LiNi0.5Mn1.5O4 and LiNi0.25Cu0.25Mn1.5O4 cathode materials.