Robust electrospun polyimide (PI) membranes are simply fabricated by polymerization of oxidianiline (ODA) and pyromellitic dianhydride (PMDA). The as-prepared PI membranes, with reliable safety (selfextinguishing) and excellent mechanical property, exhibit highly uniform morphology with an average fiber diameter similar to 600 nm, high porosity similar to 67%, high electrolyte uptake similar to 534% and good relative absorption ratio similar to 75% of the initial absorption (electrolyte uptake until 240 min). With the presence of triethylene glycol diacetate-2-propenoic acid butyl ester (TEGDA-BA) gel electrolytes, the resulting polyimide-gel electrolytes (PI-GEL) show a high ionic conductivity up to 2.0 x 10(-3) S cm(-1) at 25 degrees C, coupled with high electrochemical stability (> 4.5 V vs. Li/Li+). The Li/PI-GEL/LiFeO4 cells demonstrate remarkably stable charge/discharge performance and excellent capacity retention of similar to 146.8 mAh g(-1) (0.1 C) after 100 cycles. The results suggest a facile strategy for scalable fabrication of high-performance polymer electrolyte membrane for lithium ion batteries. (C) 2014 Elsevier Ltd. All rights reserved.