The cycling and storage behavior of LiNi0.5Mn1.5O4 and MCMB electrodes for 5-V Li-ion batteries was investigated at elevated temperatures using a variety of electrochemical (CV, EIS) and spectroscopic (XPS, micro-Raman) tools. It was established that LiNi0.5Mn1.5O4 electrodes could be cycled highly reversibly, demonstrating sufficient capacity retention at 60°C by a constant current/constant voltage mode in DMC–EC/1.5M LiPF6 solutions. By studying the influence of temperature on the impedance of LiNi0.5Mn1.5O4 electrodes, we conclude that when the initial electrode's surface chemistry is developed at a high temperature (60°C) it becomes nearly invariant, and hence, their impedance remains steady upon cycling and storage. Prolonged storage of these electrodes at 60°C may result in local Mn and Ni dissolution and transformation of the active material to λ-MnO2. We have found that the surface chemistry of aged LiNi0.5Mn1.5O4 electrodes (free of carbon black and PVdF) involves the formation of LiF, C–F and P–F x species. Storage of MCMB electrodes in LiPF6 containing solutions at open circuit conditions (before their first lithiation) leads to significant morphological changes and the formation of lithium fluoride on the electrode surface, as determined by the XRD studies. LiF is probably a product of a catalytic thermal decomposition of LiPF6. These initial changes further influence the impedance and kinetics of the lithiated electrodes.