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 degrees 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. (C) 2016 Elsevier B.V. All rights reserved.