A series of polymer electrolytes based on multiarm polymers and lithium salt complexes were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and impedance measurement. The relationships of conductivity with salt concentration, temperature, and arm numbers are discussed. It is suggested that the star polymer has a higher solvency and ion transfer ability on lithium salts than on linear polymers. The conductivity maximum appeared at a higher salt concentration ([EO]/[Li] = 4). Impedance measurement suggested that the optimum conductivity was 2 x 10(-4) s (.) cm(-1). The conductivity increased with temperature and the dependence of ionic conductivity on temperature fits the Arrhenius equation. Among the studied systems, the star polymer with a five arm number performs better than other structures. (C) 2004 Wiley Periodicals, Inc.