A perfluoroalkyl-terminated multiarm star polymer (perfluoroalkyl-terminated hyperbranched polyglycerol) was synthesized and characterized on the basis of perfluorooctanoyl chloride grafting on hyperbranched polyglycerol. The conductivity of a blend of the perfluoroalkyl-terminated star polymer and linear poly(ether urethane) was studied. The results indicated that this blend had better solvating capability in salt and higher ionic conductivity. The conductivity of the blend was 2.5 x 10(-4) S cm(-1) at 60 degrees C when the concentration of the perfluoroalkyl-terminated hyperbranched polyglycerol was 30 wt % and the ethylene oxide (EO)/Li ratio was 4 in the blend. (c) 2005 Wiley Periodicals, Inc.