Proton　conductivity　of　proton　exchange　membranes　(PEMs)　strongly　relies　on　microscopic　morphology,　which　can　be　modulated　by　engineering　the　distribution　of　ionic　groups.　Herein,　poly(arylene　ether)s　with　densely　distributed　allyl　functionalities　are　polymerized　from　a　tetra-allyl　bisphenol　A　monomer.　The　subsequent　thiol-ene　addition　with　sodium　3-mercapto-1-propanesulfonate　yields　comb-shaped　sulfonated　fluorinated　poly(arylene　ether)s　(SFPAEs)　with　ion　exchange　capacities　(IECs)　ranging　from　1.29　mmol·g−1　to　1.78　mmol·g−1.　These　SFPAEs　exhibit　superior　proton　conductivity　over　the　whole　temperature　range,　which　is　attributed　to　the　enhanced　hydrophilic/hydrophobic　phase　separation　as　evidenced　by　small　angle　X-ray　scattering　characterizations.　The　SFPAE-4-40　with　an　IEC　of　1.78　mmol·g−1　shows　the　largest　proton　conductivity　of　93　mS·cm−1　at　room　temperature　under　fully　hydrated　condition,　higher　than　that　of　Nafion　212.　Furthermore,　the　vanadium　redox　flow　battery　(VRFB)　assembled　with　SFPAE-4-40　separator　exhibits　higher　energy　efficiency　than　the　VRFB　assembled　with　Nafion　212.　©　2019,　Chinese　Chemical　Society　Institute　of　Chemistry,　Chinese　Academy　of　Sciences　Springer-Verlag　GmbH　Germany,　part　of　Springer　Nature.