A flame retardant and thermally dimensional stable membrane with high permeability and electrolyte wettability can overcome the safety issues of lithium ion batteries (LIBs) at elevated temperatures. In this work, a multifunctional thermoset nonwoven membrane composed of melamine formaldehyde resin (MFR) nano-fibers was prepared by a electro-spinning method. The resultant porous nonwoven membrane possesses superior permeability, electrolyte wettability and thermally dimensional stability. Using the electrospun MFR membrane, the LiFePO4/Li battery exhibits high safety and stable cycling performance at the elevated temperature of 120 °C. Most importantly, the MFR membrane contains lone pair electron in the nitrogen element, which can chelate with Mn2+ ions and suppress their transfer across the separator. Therefore, the LiMn2O4/graphite cells with the electrospun MFR multifunctional membranes reveal an improved cycle performance even at high temperature. This work demonstrated that electrospun MFR is a promising candidate material for high-safety separator of LIBs with stable cycling performance at elevated temperatures.