Preparation of H3PW12O40/Polyvinyl alcohol (PVA) catalytic membranes on porous ceramic plates was studied in this paper. SEM (scanning electron microscopy) and XPS (X-ray photoelectron spectrometry) were used to characterize the membrane nature. The separative and catalytic properties of the membranes were tested by the esterification of acetic acid with n-butanol. It was found that different ways of crosslinking played an obvious role in the membranes＇ performance.