Acrylonitrile/N-[4-(aminosulfonyl)phenyl]acrylamide (AN/ASPAA) copolymers were synthesized and used as a host of lithium ion conducting electrolytes. The composition, molecular weight and molecular weight distribution of AN/ASPAA copolymers were determined, and the influence of copolymer composition on the glass temperature of AN/ASPAA copolymers and the ion conductivity of electrolytes were investigated. The molecular weights of AN/ASPAA copolymers were lower than those of AN and ASPAA homopolymers due to the cross-termination reaction. The glass temperatures of AN/ASPAA copolymers increased as the molar fraction of ASPAA units in copolymers increased. The lithium ion conductivities of the polymer electrolytes increased initially as the molar fraction of ASPAA units in copolymers increased, and a maximum conductivity was achieved when the molar fraction of ASPAA in the copolymer was 16.8%.