Lithium (Li)-rich manganese (Mn)-rich oxide (LMR) cathode materials, despite of the high specific capacity up to 250 mAh g−1 suffer from instability of cathode/electrolyte interfacial layer at high working voltages, causing continuous voltage decay and capacity fading, especially at elevated temperatures. In various battery systems, localized high-concentration electrolytes (LHCEs) have been widely reported as a promising candidate to form effective electrode/electrolyte interphases. Here, an optimized LHCE is studied in graphite (Gr)-based full cells containing LMR cathode, being cycled at 25, 45 and 60 °C with the reference of a conventional LiPF6-based electrolyte. It is revealed that the LHCE can effectively suppress continuous electrolyte decompositions and mitigate the dissolution of Mn ions due to the formation of more protective electrode/electrolyte interphases on both anode and cathode, which, in turn, lead to significantly improved cycling stability and enhanced rate capability under the selected temperatures. The mechanistic understanding on the failure of the conventional LiPF6-containing electrolyte and the function of the LHCE in Gr||LMR cells under high temperatures provides valuable perspectives of electrolyte development for practical applications of LMR cathodes in high energy density batteries over a wide temperature range.