High-performance NaA zeolite membrane was synthesized on polyetherimide(PEA)-NaA zeolite/α-Al2O3 composite supports by microwave heating method. Influence of microwave heating time on membrane synthesis was mainly investigated. The as-synthesized NaA zeolite membranes were characterized by XRD and SEM. XRD results show that only NaA zeolite emerges on the composite support surface. The SEM results show the composite support surface is fully covered by uniform and compact NaA zeolite membrane. The pervaporation properties of the as-synthesized membrane were evaluated by dehydration of alcohol/water mixture. It was found that the flux decreased with the increment of the alcohol amount in the feed, separation factors were on the contrary. Pervaporation results present that separation factors were as high as 13000 at m(C2H6O) /m (H2O) = 95:5, instead, the fluxes were only 0.05 kg/(m2?h).