This study presents an evaluation of structural changes resulting from cycling modified copper/nickel LiMn2O4 spinels at 263K. In situ synchrotron XRD shows that cycling LiMn2O4 at 263K resulted in the formation of mixed cubic and tetragonal phases with a consequent lower capacity. The differential capacitance profile normally exhibiting two peaks at 298K is modified, showing only one oxidation peak at 263K in the 4V region. The changes observed are attributed to interactions between Jahn–Teller active Mn3+ species and Li+ ions. These changes are not observed once copper/nickel modified spinels are being evaluated, because of the decrease in Mn3+ population. All the observed changes are fully reversible once the material is cycled back at 298K.