In order to overcome severe capacity fading of LiMn2O4/graphite Li-ion cells at high temperature at 60 °C, fluoroethylene carbonate (FEC) was newly evaluated as an electrolyte additive. With 2 wt.% FEC addition into the electrolyte (EC/DEC/PC with 1 M LiPF6), the capacity retention at 60 °C after 130 cycles was significantly improved by about 20%. To understand the underlying principle on the capacity retention enhancement, the electrochemical properties of the cells including cell performance, impedance behavior as well as the characteristics of the interfacial properties were examined. Based on these results, it is suggested that the improved capacity retention of LiMn2O4/graphite Li-ion cells with addition of FEC especially at high temperature is mainly originated from the thin and stable SEI layer formed on the graphite anode surface.