Inspired by the bioadhesion phenomena and principle, the composite membranes with hyaluronic acid (HA) bioadhesive as the active layer were facilely fabricated, which exhibited desirable structural stability, high water sorption and water retention capacity. The physicochemical properties, including morphology, wetting characteristic, cross-linking structure, and thermal stability were characterized and assessed by FESEM, contact angle measurement, FT-IR, and TGA. The interfacial adhesion strength and adhesion mechanism were probed by T-peel test and molecular dynamics (MD) simulation. The impacts of different ultrafiltration support layers, amount of HA and glutaraldehyde (GA) in casting solutions on the pervaporation performance were explored. Using the hydrophilically modified-polyacrylonitrile (HM-PAN) ultrafiltration membrane as the support layer, when the concentration of HA solution was 0.8 wt%, and the molar ratio of GA to HA monomer unit was 0.3, the composite membrane showed the permeation flux of 1.634 kg/(m(2) h) and the separation factor of 233 for 90 wt% aqueous ethanol solution at 353 K. Furthermore, the effect of water concentration in the feed on the separation performance and the long-term operation stability of the membranes were investigated. (C) 2010 Elsevier B.V. All rights reserved.