Polymer electrolytes based on electrospun polyimide (PI) membranes are incorporated with electrolyte solution containing 1molL−1 LiPF6/ethylene carbonate/ethylmethyl carbonate/dimethyl carbonate to examine their potential application for lithium ion batteries. The as-electrospun non-woven membranes demonstrate a uniformly interconnected structure with an average fiber diameter of 800nm. The membranes, showing superior thermal stability and flame retardant property compared to the commercial Celgard® membranes, exhibit high porosity and high uptake when activated with the liquid electrolyte. The resulting PI electrolytes (PIs) have a high ionic conductivity up to 2.0×10−3 S cm−1 at 25°C, and exhibit a high electrochemical stability potential more than 5.0V (vs. Li/Li+). They also possess excellent charge/discharge performance and capacity retention. The initial discharge capacities of the Li/PIs/Li4Ti5O12 cells are 178.4, 167.4, 160.3, 148.3 and 135.9 mAh g−1 at the charge/discharge rates of 0.2C, 1C, 2C, 5C and 10C, respectively. After 200 cycles at 5C, a capacity around ∼146.8 mAh g−1 can be still achieved. The PI-based polymer electrolytes with strong mechanical properties and good electrochemical performance are proved to be promising electrolytes for lithium ion batteries.