The proton exchange membrane fuel cells should have three major advantages: 1. micro-phase separation, 2. mechanical properties and 3. thermal stability. According to the recent literature and the material of core benzene ring poly (arylene ether)s studied by our group, this paper synthesize a series of the locally and densely sulfonated polymer. We use core benzene ring as the diol monomer and the containing CF3 groups as the fluorine monomer to synthesis poly (arylene ether)s via nucleophilic displacement reactions, and then use the different concentrations synthesized sulfonated polymer by sulfonic acid reaction. According to NMR¡¦s result we confirmed that the structure of synthetic materials is correct. By using GPC we get that the KP1, KP2, and KP3¡¦s molecular weight about 20000 (g/mol) ; The thermal stability up to 530OC for 5% loss in TGA under nithtrogen, to prove thisseries of polymer excellent thermal stability. After sulfonation, SKP1, SKP2 and SKP3¡¦s decomposition temperature decreased about 200OC ~ 250OC ranging with increasing degree of sulfonation. By DSC analysis, K1, K2 and K3 monomer's Tg followed up with the increase of the benzene ring number, however, the polymer does not have any apparent peak. About the Proton conductive, SKP2C IEC 2.23mequiv / g, water uptake 94%, the highest proton conductivity can be as high as 68.2 mS / cm, has been similar to Nafion 117 of 70 mS / cm.