Environmentally friendly polymer electrolyte membrane was prepared by emulsion polymerization via interpenetrating network technology. The physicochemical property of the prepared polymer membrances were characterized by Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), mechanical strength measurements, thermal analysis, electrochemical impedance spectroscopy (EIS) and charge-discharge test. The results showed that the as-prepared polymer membrane M2 exhibited a mechanical strength of 7.53 MPa and elongation of 90.4%, uptake electrolyte 150%, thermal shrinkage 4% with ionic conductivity of 0.98 mS/cm at 25 ℃ when the mass ratio of m(AMPS):m(BA):m(AA):m(AN) was 1:3:2:2, demonstrating the best mechanical and electrochemical properties. The polymer electrolyte membrane has good compatibility and universality with the anode and cathode materials current mainstream used in lithium-ion batteries. The LiCoO₂ as cathode active material had an initial discharge capacity of 141.3 mA.h/g, while the graphite as cathode active material possessed an initial discharge capacity of 347.1 mA.h/g, and their corresponding discharge capacity retention were 94.8% and 85.0% after 100 cycles at 0.1 C rate. The battery delivered a discharge capacity of 119.8 mA.h/g and 239 mA.h/g based on the LiCoO₂ and graphite in the cathode at 2.0 C rate, indicating that the prepared material exhibited excellent electrochemical performances.