New proton exchange membranes were prepared and evaluated as polymer electrolytes for a proton exchange membrane fuel cell (PEMFC). Two types of fluorinated poly(arylene ether)s (FPAEs) were synthesized by nucleophilic aromatic substitution of decafluorobiphenyl (DFBP) with 4,4′-(hexafluoroisopropylidene)diphenol (HFDP) and bisphenol-A (BPA). The FPAEs so prepared were converted into proton exchange polymers by sulfonation with fuming sulfuric acid (30% SO3). The FPAEs and sulfonated-fluorinated poly(arylene ether)s (S-FPAEs) with various sulfonation levels were characterized using 1 H NMR, thermogravimetric analysis (TGA) and back titration, and then successfully evaluated as proton exchange membranes (PEM) with unit cell operation. power output measurements of S-DFBP-HFDP carried out at a cell temperature of 80°C. They exhibited a maximum power density of 425.5mW/cm2 at 1150mA/cm2.