We synthesized novel sulfonated star-hyperbranched polyimides composed of a hydrophobic hyperbranched polymer for polymer stability and a hydrophilic sulfonated polyimide as the proton-transport site in the core-shell structure. The proton conductivities of the star-hyperbranched polyimide membranes were measured as functions of the relative humidity and temperature using electrochemical impedance spectroscopy. Although the water uptake and IEC value for the sulfonated star-hyperbranched polyimide membranes were almost constant, the proton conductivity of the membrane strongly depended on the molecular weight of the hydrophilic sulfonated polyimide as the shell. Especially, the conductivity of the high molecular weight star-hyperbranched polyimide membranes was significantly superior to that determined in Nafion (R) at all temperatures and was 0.51 S cm(-1) at 80 degrees C and 98% RH, which may suggest that a good proton-transport pathway in the core-shell structure is formed. Consequently, this material proved to be promising as a proton exchange membrane and may have potential applications for use in fuel cells. (C) 2010 Elsevier B.V. All rights reserved.