Abstract: Catalytic and separative difunctional hollow fiber composite membranes were prepared using polyacrylonitrile (PAN) hollow fiber membrane as support, polyvinyl alcohol (PVA) as separative layer, and perfluorosulfonic acid resin (PFSA) as catalytic layer where nanosized SiO2 was embedded. The surface performances of difunctional membranes such as water contact angles, mechanical properties, separation performances and catalytic performances for the acetic acidethanol esterification were investigated. The results showed that the catalytic and separative difunctional membranes had good mechanical properties and hydrophilicity with a permeation flux of 175 g/(m2·h) and the corresponding selectivity of 144. Compared with blank, the conversion of acetic acidethanol esterification increased significantly by using difunctional membranes. The time to reach equlibrum conversion reduced, and the conversion could reach 60%.