The development of hydrogen energy systems has placed a high demand on hydrogen-permeable membranes as compact hydrogen separators and purifiers. Although Pd/Ceramic composite membranes are particularly effective in this role, the high cost of these membranes has greatly limited their applications; this high cost stems largely from the use of expensive substrate material. This problem may be solved by substrate recycling and the use of lower cost substrates. As a case study, we employed expensive asymmetric microporous Al2O3 and low-cost macroporous symmetric Al2O3 as membrane substrates (average pore sizes are 0.2 and 3.3 mu m, respectively). The palladium membranes were fabricated by electroless plating, and substrate recycling was carried out by palladium dissolution with a hot HNO3 solution. The functional surface layer of the microporous Al2O3 was damaged during substrate recycling, and the reuse of the substrate led to poor membrane selectivity. With the assistance of pencil coating as a facile and environmentally benign surface treatment, the macroporous Al2O3 can be successfully utilized. Furthermore, the macroporous Al2O3 can be also recycled and reused as membrane substrate, yielding highly permeable, selective and stable palladium membranes. Consequently, the substrate cost can be further decreased, and the applications of this kind of membranes would expand. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.