The　microstructure　of　polymer　electrolyte　membranes　plays　a　key　role　in　ion　conductivity　and　water　transport.　Herein,　fluorinated　poly(aryl　ether)s　with　tetra-alkylsulfonate　side　chains　(SFPAEs)　have　been　successfully　synthesized　from　the　copolymerization　of　a　newly　developed　tetra-allyl-containing　bisphenol　(TABP)　monomer,　followed　by　the　thiol-ene　addition　with　sodium　3-mercapto-1-propanesulfonate　to　attach　the　ionic　groups　at　the　end　of　the　flexible　chains.　Being　the　first　of　its　kind,　the　densely　distributed　and　lengthy　alkylsulfonate　group　possesses　the　benefit　of　ease　to　self-assemble　into　hydrophilic　domains　during　membrane　preparation　via　solution　casting.　Indeed,　the　TEM　characterizations　revealed　that　distinct　hydrophilic　channels　of　similar　to　1　-　2　nm　width　had　been　formed,　much　larger　than　those　of　a　home-made　control　sample　where　only　di-alkylsulfonate　side　chains　were　attached.　The　SFPAE-4-45　with　an　IECw　of　2.0　mmol　g(-1)　exhibited　an　enhanced　proton　conductivity　of　143.7　mS　cm(-1)　at　room　temperature,　which　was　superior　to　that　of　Nafion　212　(91.0　mS　cm(-1)).　Furthermore,　the　oxidative　stabilities　of　SFPAEs　were　significantly　higher　than　those　of　non-fluorinated　analogs　in　literature.　This　study　offered　a　new　route　to　engineering　the　pendent　structure　of　ionomers　for　well-defined　microscopic　morphologies.　(C)　2019　Science　Press　and　Dalian　Institute　of　Chemical　Physics,　Chinese　Academy　of　Sciences.　Published　by　Elsevier　B.V.　and　Science　Press.　All　rights　reserved.