Metalorganic frameworks (MOFs), as a newly developed family of crystalline microporous materials, have attracted considerable attention as promising candidates for the fabrication of superior molecular sieve membranes. For the synthesis of MOF membranes, the MOF's characteristics, such as pore size, stability, and adsorption affinity, have to be considered carefully. In this work, we prepare a highly hydrophobic and permselective Zn(BDC)(TED)(0.5) membrane for H-2/CO2 separation through secondary growth method with seeding. Attributed to the preferential adsorption affinity and capacity to CO2 as well as a highly porous structure with large channels, the Zn(BDC)(TED)(0.5) membrane displays a high H-2/CO2 permselectivity. For the separation of an equimolar H-2/CO2 mixture at 180 degrees C and 1 bar, a H-2 permeance of 2.65x10(-6) mol m(-2) s(-1) Pa-1 and a H-2/CO2 selectivity of 12.1 are obtained. Furthermore, because of its high hydrophobicity, the pore volume of Zn(BDC)(TED)(0.5) is not blocked in the presence of steam, which is promising for potential applications of hydrogen separation and purification. (C) 2013 Elsevier B.V. All rights reserved