Achieving　strong　interaction　with　the　targeted　composition　and　constructing　abundant　transport　channels　is　crucial　to　obtain　the　pervaporation　(PV)　membrane　with　high　selectivity　and　flux.　Here,　three　ionic　liquids　(ILs)　were　screened　out　based　on　their　relative　selectivity　and　capacity　targeting　for　bioethanol　dehydration　by　COSMO-RS.　The　interaction　energies　analysis　between　ILs,　EtOH,　and　H2O　suggests　that　the　ILs　can　form　strong　hydrogen　bonds　with　water　and　disrupt　the　hydrogen　bond　in　the　EtOH–H2O　azeotropic　mixture,　which　is　beneficial　for　improving　the　selectivity.　Furthermore,　driven　by　the　multiple　hydrogen　bonds,　electrostatic　interactions,　and　van　der　Waals　forces,　ILs　could　self-assemble　with　polyvinyl　alcohol　(PVA)　to　fabricate　the　PV　membrane　with　well-ordered　micelle　nanostructure,　as　its　structure　was　revealed　by　MD　simulations.　The　formation　of　the　ILs-PVA　micelle　dramatically　influenced　membrane　surface　morphology,　roughness,　and　water　contact　angle,　providing　an　extra　transport　channel　for　the　membrane.　The　optimal　membrane　(at　the　cmc　point)　exhibited　a　superior　ethanol　dehydration　separation　factor　of　1627,　along　with　a　flux　of　684　g/m2h　at　50　°C.　It　can　be　expected　that　this　novel　self-assembled　ILs-PVA　micelle　nanostructure　strategy　will　find　promising　applications　in　other　azeotropic　mixture　separation　processes,　like　ethanol-ethyl　acetate,　water-butanol,　etc.　©　2024　Elsevier　B.V.