NaA zeolite membranes were prepared by secondary growth method on the outer surface of alpha-Al2O3 hollow fiber supports. Vacuum seeding method was used for planting zeolite seeds on the support surfaces. Hydrothermal crystallization was then carried out in a synthesis solution with molar ratio of Al2O3:SiO2:Na2O:H2O = 1:2:2:120 at 100 degrees C for 4 h. Effects of seeding conditions on preparation of hollow fiber NaA zeolite membranes were extensively investigated. Moreover, hollow fiber membrane modules with packing membrane areas of ca. 0.1 and 0.2 m(2) were fabricated to separate ethanol/water mixture. It is found that the thickness of seed layer is obviously affected by seed suspension concentration, coating time and vacuum degree. Close-packing seed layer is required to obtain high-quality membranes. The optimized seeding conditions (seed suspension mass concentration of 0.5%-0.7%, coating time of 5 s and vacuum degree of 10 kPa) lead to dense NaA zeolite layer with a thickness of 6-8 mu m. Typically, an as-synthesized hollow fiber NaA zeolite membrane exhibits good pervaporation performance with a permeation flux of 7.02 kg.m(-2).h(-1) and separation factor >10000 for separation of 90% (by mass) ethanol/water mixture at 75 degrees C. High reproducibility has been achieved for batch-scale production of hollow fiber NaA zeolite membranes by the hydrothermal synthesis approach. (C) 2015 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.