Segmented polyurethanes with perfluoropolyether(PFPE) and poly(ethylene oxide) blocks were synthesized by reacting a fluorinated macrodiol and poly(ethylene glycol) (PEG) in different ratios with methylenebis(phyenyleneisocyanate) (MDI) in the presence of a solvent. Thermal and ionic conductivities were studied as a function of fluorine content of Polyurethanes. The chemical structures were characterized by Fourier transform infrared, NMR spectroscopies, and thermal and mechanical properties of FPU investigated by differential scanning calorimetry and dynamic mechanical analysis. The surface properties were analyzed by using contct angle meter. The ionic conductivity of FPU-LiCF₃SO₃ complexs were investigated through changes in the polymer composition. The relative molar ration of PFPE and PEG in the polymer played an important role in the conductivity and thermal properties.