A series of tetra-sulfonated poly(arylene ether)s are prepared from a new tetra-sulfonated difluoride monomer and commercial 4,4'-difluorobenzophenone and 4,4'-(hexafluoroisopropylidene)diphenol via polycondensation process. With the content of tetra-sulfonated monomer raising from 15% to 35% in difluoride monomer, sulfonated polymers with ion exchange capacity (IEC) ranging from 0.92 to 1.66 mequiv g(-1) are obtained. The high thermal stable polymer owns the glass transition temperature higher than 190 degrees C and onset decomposition temperature higher than 300 degrees C. The polymers exhibit good solubility in dimethylacetamide (DMAc) and the tough, flexible and transparent films are obtained by solution casting method. These membranes exhibit suitable proton conductivity, low methanol permeability and excellent dimensional stability. The membrane with IECE = 1.81 mequiv g(-1) shows considerable proton conductivity (84 mS cm(-1)) and swelling ration (only 8.6%) under fully hydrated state at 100 degrees C. Their excellent performance is attributed to distinct phase separation between hydrophilic and hydrophobic morphology, which is observed by TEM. This work demonstrates that the strategy of combining locally high densities hydrophilic segment with fluorine-containing hydrophobic segment in a polymer chain can balance on proton conduction and dimensional stability efficiently. Furthermore, these membranes own much lower methanol permeability and higher selectivity than Nafion. (C) 2012 Elsevier B.V. All rights reserved.