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 (self-extinguishing) and excellent mechanical property, exhibit highly uniform morphology with an average fiber diameter ∼ 600nm, high porosity ∼67%, high electrolyte uptake ∼534% and good relative absorption ratio ∼75% of the initial absorption (electrolyte uptake until 240min). 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 2.0×10−3 Scm−1 at 25°C, coupled with high electrochemical stability (>4.5V vs. Li/Li+). The Li/PI-GEL/LiFeO4 cells demonstrate remarkably stable charge/discharge performance and excellent capacity retention of ∼146.8mAhg−1 (0.1C) after 100 cycles. The results suggest a facile strategy for scalable fabrication of high-performance polymer electrolyte membrane for lithium ion batteries.