Abstract: How to prepare high-performance separation membranes with morphology controlled and well-dispersed nanoparticles, has been a hotspot and difficulty in the field of membrane separation. Mixed matrix membranes were prepared by crosslinking polyvinyl alcohol (PVA), maleic acid (MA) and SiO₂ via an aqueous sol-gel route and solution casting method. The membrane was characterized by SEM, FTIR, XRD and tested for its perfor-mance in pervaporation separation of ethanol/water mixtures with feed ethanol concentration of 97wt% at 50℃. Membrane characterization results reveal that SiO₂/crosslinked PVA membrane shows that elliptic leaves SiO₂ nano-particles cover the surface and act as a water prescreening layer, are well disperse within the polymer matrix. It results in a significantly enhanced effect in both flux and selectivity. The membranes achieve high water flux of 0.072 kg·m⁻²·h⁻¹ and separation factor of 12301 for separation of 97wt% ethanol aqueous solution. The enhanced membrane performance can be attributed to the surface prescreening ability and dense crosslinking membrane network. The research results would promote the study of SiO₂/PVA composite materials, and their application in the field of membrane separation.