Acetic　acid,　as　one　of　the　top　50　important　chemicals,　has　been　broadly　applied　for　production　of　cellulose　acetate,　polyvinyl　acetate,　as　well　as　synthetic　fibers　and　fabrics,　and　so　on.　However,　the　acetic　acid　production　always　involves　in　water　which　should　be　removed.　Thus,　energy-efficient　and　environmental-friendly　dehydration　of　acetic　acid　is　highly　required　in　current　chemical　industry.　In　this　study,　we　proposed　a　＇hard-crosslinking-soft＇　strategy　to　construct　a　kind　of　organic-inorganic　hybrid　membrane　by　doping　aminated　silica　(SiO2-NH2)　nanoparticles　into　the　polyelectrolyte　complex　(PEC)　membrane　for　dehydration　of　acetic　acid.　The　addition　of　SiO2-NH2　nanoparticles　plays　two　roles:　one　is　as　the　＇hard＇　part　to　overcome　the　over-swelling　issue　of　＇soft＇　PEC　membrane;　another　is　creation　of　more　free　volume　for　water　passing　through.　As　a　result,　the　proposed　hybrid　membrane　could　simultaneously　augment　the　permeability　and　selectivity　of　the　pervaporation　membrane,　breaking　the　notorious　＇trade-off＇　restriction　of　separation　membranes.　The　preparation　parameters　and　operation　condition　on　the　performance　of　the　membrane　were　detailed　studied.　The　optimized　membrane　offers　a　flux　of　1225　g/m2h　and　a　separation　factor　of　1442　in　dehydration　of　10　wt%　water/acetic　acid　mixtures　at　50　degrees　C,　with　pervaporation　separation　index　of　1.77　x　106　g/m2h,　among　the　top-tier　separation　performance.　Besides,　the　prepared　membrane　could　stably　work　for　144　h　due　to　the　chemical　crosslinking　by　glyoxal,　promising　for　the　practical　application　for　acetic　acid　dehydration.