A heat-resistant and rigid-flexible coupling glass-microfiber nonwoven supported cyanoethyl-β-polyvinyl alcohol composite polymer electrolyte membrane (GFMPE) has been successfully fabricated explored for high-performance lithium batteries. It was demonstrated that the GFMPE possessed enhanced mechanical property, superior dimensional thermostability (>200°C). In addition, Ethylene carbonate (EC)/Dimethyl carbonate (DMC) solvent soaked GFMPE exhibited a superior Li ion transport number of 0.86, wide electrochemical window up to 4.8V vs Li+/Li and high ionic conductivity of 0.89mS/cm at 25°C. Moreover, LiCoO2/graphite cells using such polymer electrolyte with EC:DMC (1:1, v/v) showed excellent cycling stability and superior rate capability at room temperature. It is important to note that the LiFePO4/Li cell using GFMPE/propylene carbonate (PC) can also operate very well at an elevated temperature of 120°C. These fascinating results would endow GFMPE a very promising polymer electrolyte in high-performance lithium batteries with improved safety and reliablity.