A cross-linked polymer electrolyte membrane (SPE) was fabricated by a solvent-free hot-pressing method for all-solid-state lithium ion battery. The ionic conductivity of the electrolyte is 1.34 x 10(-3) S cm(-1) and the decomposition potential is 4.87 V at the ethylene oxide (EO):LiN(SO2CF3)(2) (LiTFSI) molar ratio of 20:1 and 120 degrees C. TG-DSC results show that the SPE is thermally stable up to 230 degrees C in argon atmosphere. The assembled LiFePO4/SPE/Li all-solid-state battery can stably work in the temperature range of 80-140 degrees C. At 120 degrees C, the initial discharge capacity of the battery is 156.7 mAh g(-1) at 1C which is close to the theoretical capacity of the cathode material, showing that the solvent-free filming method is low-cost and environment-friendly for solid polymer electrolyte and all-solid-state lithium ion battery. (C) 2015 Elsevier B.V. All rights reserved.