Catalytic disks of porous ceramic plates supported H3PW12O40 were prepared. Cross-linked poly vinyl alcohol (PVA) composite membranes using the catalytic disks as the matrixes were obtained by spin coating, The dehydration reaction of butanediol (BD) to form tetrahydrofuran (THF) was taken as a model reaction to testify the catalytic activity of the disk, and which was found to be a good catalyst compared with the original H3PW12O40. The separative properties of the membrane were also examined by pervaporation using the same reacting mixture, and the water content in the reactor was much less than THF during the reaction coupled pervaporation.