A random copolymer P(VAc-MMA) was synthesized via seeded emulsion copolymerization with vinyl acetate (VAc) and methyl methacrylate (MMA) as monomers, and the polymer electrolytes comprising blend of corresponding copolymer P(VAc-MMA) as a host polymer and LiClO4 as a dopant were prepared by solution casting technique. Performances of the synthesized copolymer and prepared polymer membrane and electrolyte were studied by FTIR, XRD, TG, DSC, mechanical testing and AC impedance. According to the study of FTIR and DSC, it was found that P(VAc-MMA) had been formed. XRD indicates that the amorphous nature in copolymer increased with increasing the ratio of VAc in monomers, resulting in expedite migration of ions. The polymer electrolytes based on P(VAc-MMA) possess excellent thermal stability, fine mechanical performance and high ionic conductivity. The maximum ionic conductivity value was found to reach 1.27 × 10－3 S·cm－1 at 25°C. The temperature dependence of the polymer electrolyte complexes appeared to obey Arrhenius equation.