Using pyridine as template, polycrystalline Na-ferrierite membrane with thickness of about 30μm was prepared successfully on macroporous α-Al 2 O 3 support in a short crystallization time by conventional and vacuum-assisted secondary growth. The effects of synthesis parameters such as template, alkalinity and dilution were investigated. The characterization and properties of Na-ferrierite membrane prepared using parent gel with molar composition of 1Al 2 O 3 :60SiO 2 :6Na 2 O:1835H 2 O:64C 5 H 5 N were detected. The three-stage synthesized Na-ferrierite membrane had the best properties with the single-gas permeances of H 2 >CH 4 >O 2 >N 2 >CO 2 >C 3 H 8 >SF 6 . The separation properties of Na-ferrierite membrane were evaluated by benzene/p-xylene pervaporation test. With increasing the benzene feed concentration, the fluxes of benzene and p-xylene increased and decreased, respectively, and the separation factor decreased firstly and increased afterward. Furthermore, the formation mechanism of the compact Na-ferrierite membrane was proposed.