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.