Hydrogen-based energy system could address issues related to global climate change, energy security, and local air pollution. Thermally and hydrothermally stable microporous membranes with intrinsic high H(2)/CO(2) selectivity are highly demanded. A novel zeolitic imidazolate framework (ZIF-7) membrane was tested for its gas separation performance. ZIFs are microporous materials and belong to the new class of metal-organic frameworks (MOFs). ZIF-7 is formed by bridging benzimidazolate anions and zinc cations resulting in a sodalite (SOD) topology with a pore size of about 0.3 nm. The ZIF-7 membrane exhibited promising H(2) separation abilities. At 220 degrees C, the H(2) permeance is similar to 4.5 x 10(-8) mol m(-2) s(-1) Pa(-1) and the mixture separation factors for H(2)/CO(2), H(2)/N(2), and H(2)/CH(4) are 13.6, 18.0, and 14.0, respectively. As a result of molecular sieving mechanism, the ideal selectivities and mixture separation factors are identical. The permeation of H(2) through the ZIF-7 membrane is highly activated with an apparent activation energy of 11.9 kJ mol(-1). Due to the ultra-hydrophobic properties of ZIF materials, the ZIF-7 membrane also showed excellent hydrothermal stability in the presence of steam. Our results clearly demonstrate that ZIF-7 membranes have an intrinsic high H(2)/CO(2) selectivity and a promising application in hydrogen separation, which is based on its very narrow and well-defined crystal pore structure. (C) 2010 Elsevier B.V. All rights reserved.