Poly(acrylonitrile–butyl acrylate) gel polymer electrolyte was prepared for lithium ion batteries. The preparation started with synthesis of poly(acrylonitrile–butyl acrylate) by radical emulsion polymerization, followed by phase inversion to produce microporous membrane. Then, the microporous gel polymer electrolytes (MGPEs) was prepared with the microporous membrane and LiPF6 in ethylene carbonate/diethyl carbonate. The dry microporous membrane showed a fracture strength as high as 18.98MPa. As-prepared gel polymer electrolytes presented ionic conductivity in excess of 3.0×10−3 Scm−1 at ambient temperature and a decomposition voltage over 6.6V. The results showed that the as-prepared gel polymer electrolytes were promising materials for Li-ion batteries.