An amphiphilic hyperbranched-star polymer (HPE-g-MPEG) was synthesized by grafting methoxy poly (ethylene glycol) to the end of the hyperbranched polyester (HPE) molecule using terephthaloyl chloride (TPC) as the coupling agent. The synthesized amphiphilic hyperbranched-star polymer was blended with poly(vinylidene fluoride) (PVDF) to fabricate porous membranes via typical phase inversion process, and then the membranes were filled and swollen by a liquid electrolyte solution to form polymer electrolytes. The influences of HPE-g-MPEG on the morphology, crystallinity, liquid electrolyte uptake, mechanical properties of the porous membranes and the electrochemical properties of the activated membranes were investigated. It was found that the addition of HPE-g-MPEG resulted in a significant increase in porosity and a considerable reduction in crystallinity of the blend membranes, which favored the liquid electrolyte uptake and, consequently, led to a remarkable increase in ion conductivity at ambient temperature. The maximum ion conductivity observed in this study was 1.76 x 10(-3)S/cm at 20 degrees C for the blend membrane with a HPE-g-MPEG/PVDF ratio of 3/10 (w/w). (C) 2009 Elsevier B.V. All rights reserved.