PAN hollow fiber ultrafiltration membrane was used as support, PVA surface-crosslinked with GA was used to prepare pervaporation layer and PFSA embedded with TiO2 or Al2O3 nano particles was used as catalytic layer, to prepare catalytic and pervaporation difunctional composite membranes. Difunctional composite membranes were evaluated by dehydration of the top product (water, ethanol and ethyl acetate ternary azeotropic system) of reactive distillation, esterification of acetic acid with ethanol, hydrophilicity and mechanical performance. It was found that difunctional composite membranes had good mechanical properties and hydrophilicity, the permeation flux could reach to 179 g/m2 h with the separation factor of water to ethanol of 95 ,no ethyl acetate in the permeate, and the time to achieve the same conversion of esterification was remarkably reduced than blank control.