In this work, we studied the cycling performance of initially inactive Li2MnO3 electrodes prepared from micron-sized particles, at 30°C and 60°C and possible structural transitions that this material can undergo due to de-lithiation. It was found that being activated at elevated temperatures, Li2MnO3 electrodes demonstrate a steady-state cycling behavior and reasonable capacity retention after aging at 60°C. The main gases evolved during polarization of the Li2MnO3 electrodes are O2 evolved from the structure and CO2 and CO that can be formed due the reaction of oxygen with carbon black. It was found that a transformation of the Li2MnO3 layered structure into a spinel-like phase occurred during the initial charging of the Li2MnO3 electrodes, which were characterized as possessing domains of both layered and spinel-like structures. The results of the structural studies of these electrodes obtained by the X-ray diffraction and transmission electron microscopy were found to be in agreement with their Raman spectroscopic responses. We suggest that the mechanism of the charge compensation during the extraction of lithium at 60°C involves both oxygen removal from the Li2MnO3 structure and the exchange between Li+ and protons formed during the anodic oxidation of ethylene carbonate or dimethyl carbonate solvents in LiPF6 solutions at high potentials (>4.5V). It is assumed that the proton-containing structure Li2−x H x−y MnO3−0.5y is retained in a discharged state of the electrode and may decompose above 500°C with the formation of Li2O and manganese oxides accompanied by the release of water and CO2.