A high-performance organosilica membrane was prepared via sol-gel processing for use in methylcyclohexane (MCH) dehydrogenation to produce high-purity hydrogen. The membrane showed a high H-2 permeance of 1.29 x 10(-6) mol m(-2) s(-1) Pa-1, with extremely high H-2/C3H8 and H-2/SF6 selectivities of 6680 and 48,900, respectively, at 200 degrees C. The extraction of hydrogen from the membrane reactor led to the MCH conversion higher than the thermodynamic equilibrium, with almost pure hydrogen obtained in the permeate stream without considering the effect of carrier gas and sweep gas in the membrane reactor, and the organosilica membrane reactor was very stable under the reaction conditions employed. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.