Pervaporation　as　a　tool　to　remove　the　residual　water　in　biological　resources,　such　as　fusel　oils　(by-product　of　alcohol　fermentation),　is　gaining　increasing　importance　and　consist　with　sustainable　development　well.　In　this　study,　polyelectrolyte　complexes/silica　(PEC/SiO2)　hybrid　hollow　fiber　membranes　were　prepared　in　situ　via　solgel　process　on　polysulfone　ultrafiltration　support　membrane..-glycidyloxypropyltrimethoxysilane　(GPTMS)　was　introduced　as　precursor　and　crosslinker　into　poly　(diallyldimethylammonium　chloride)-sodium　carboxymethyl　cellulose　complexes　to　form　SiO2　particles　in　situ　and　enhance　the　interaction　between　inorganic　and　organic　components.　The　physicochemical　properties　and　morphology　of　the　membranes　were　characterized　by　FT-IR,　FESEM,　EDS,　etc.　PEC/SiO2　membrane　(PECM/SiO2)　achieved　an　enhanced　flux　compared　with　the　PEC　pristine　membrane　without　GPTMS.　The　membranes　possessed　a　flux　of　1332　g/m(2)　h　and　water　content　in　permeate　of　99.0　wt%　for　the　dehydration　of　fusel　oils　at　60　degrees　C.　The　effects　of　feed　temperature　and　water　content　in　feed　on　pervaporation　performance　were　also　investigated.　Furthermore,　the　performance　of　PECM/SiO2　for　the　batch　continuous　dehydration　application　of　fusel　oils　was　more　efficient　than　PERVAP-1001　commercial　membranes.　This　approach　provided　a　convenient　way　to　prepare　PEC/SiO2　hybrid　hollow　fiber　membranes,　which　were　potentially　applied　in　fusel　oils　pervaporation　dehydration　processes.