Abstract The separation characteristics of the crosslinked polyvinyl alcohol (PVA) membranes prepared in our laboratory were studied by pervaporation separation of the liquid mixtures of both water/acetic acid and water/acetic acid/ n-butanol/butyl acetate. The permeation fluxes of water and acetic acid as a function of compositions were presented. The esterification of acetic acid with n-butanol catalyzed by Zr(SO 4)·4H 2O was carried out at a temperature range of 60–90°C. A kinetic model equation was developed for the esterification; then, it was taken as a model reaction to study the coupling of pervaporation with esterification. Experiments were conducted to investigate the effects of several operating parameters, such as reaction temperature, initial molar ratio of acetic acid to n-butanol, ratio of the membrane area to the reacting mixture volume and catalyst concentration, on the coupling process.