Diffusion　dialysis　(DD)　for　acid　recovery　is　significantly　restricted　by　the　poor　acid　dialysis　coefficient　((Formula　presented.))　of　anion　exchange　membranes　(AEMs).　To　overcome　such　problem,　porous　AEMs　with　extremely　high　free　space　volume　have　been　fabricated　herein　based　on　porous　membrane　substrate,　drawing　inspiration　from　the　dissolution-diffusion　concept.　Specifically,　chloromethylated　polyethersulfone　(CMPES)　has　been　used　as　the　starting　material　to　create　the　porous　substrate　via　non-solvent　phase　inversion,　then　in-situ　crosslinked　and　quaternized　using　ethylenediamine　(EDA)　and　N-methylimidazole　(NMI),　respectively.　In　this　study,　the　degrees　of　modification　of　EDA　and　NMI　are　controlled　to　adjust　the　microstructure　and　DD　performance　of　the　produced　porous　AEMs.　The　ideal　AEM＇s　(Formula　presented.)　and　acid/salt　separation　factor　(S)　are　4.3　and　2.6　times　greater,　respectively,　than　those　of　the　commercial　DF-120　membrane　at　the　same　condition.　Additionally,　it　shows　strong　organic　solvent　resistance　and　thermal　stability,　and　therefore　demonstrate　the　potential　for　widespread　use.　©　2022　Wiley　Periodicals　LLC.