The esterification of acetic acid is an important industrial process for the synthesis of ethyl acetate. A membrane reactor with a sulfonated polyethersulfone/polyethersulfone/non-woven fabrics composite catalytic coupled with a poly(vinyl alcohol) pervaporation membrane was applied in continuous esterification of ethanol with acetic acid in a flow-through mode. High equilibrium conversion was obtained for esterification in a closed-loop mode. For the pervaporation-assisted esterification in this mode, the experimental conversion was very close to the theoretical value.