Hydrophilic ZSM-5 zeolite membranes were successfully prepared using coal fly ash as aluminum source by conventional and microwave-assisted hydrothermal syntheses. As-synthesized membranes had good H2O selectivity for dehydration of 10 wt % H2O/organic solution by pervaporation. Microwave-assisted synthesis drastically reduced the membrane synthesis time from 6 to 1 h. Moreover, the flux of the membrane prepared by the microwave-assisted synthesis was about twice the flux of a membrane prepared by a conventional method.