A novel porous alumina monolithic material was prepared through the anodization technology, and its catalytic performance for hydrolysis of dimethyl ether (DME) was investigated. The anodic gamma-Al2O3 exhibited higher catalytic activity due to its stronger acidity, better hydrophilicity and lower activation energy than the commercial gamma-Al2O3 and also showed good stability in a 110 h test. Meanwhile, a series of Cu/anodic gamma-Al2O3 catalysts were prepared by impregnation method, and the mechanism of Cu loading was studied. Furthermore, the effect of Cu loading and CuO crystallite size on the activity of catalyst for DME steam reforming was investigated. The experimental results show that the conversion of DME was related to both of the Cu loading and the CuO crystallite size, while the selectivity of CO was very sensitive to the latter. In addition, the synergetic effects of different catalysts on DME steam reforming reaction system were also discussed. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.