A structured catalyst prepared by copper doping a support composed of mesoporous Co(OH)(2)/Co3O4 nanowire arrays hydrothermally grown on a stainless steel mesh was used for the methanol decomposition reaction. When copper doping was applied to an uncalcined cobalt-based support, followed by calcination in air, the catalytic activity of the resulting bimetallic catalyst was observed to increase by about one order of magnitude with respect to that of the catalyst obtained by copper doping a calcined support. This high activity, which is accompanied by a very high selectivity to CO and a fair stability, is thought to be due to the transformation of a large proportion of the copper precursor into Cu2O of a low crystal size during calcination. Comparison with other catalysts reported in the literature shows that the most active catalysts prepared in this work are better than the most active, selective and stable transition metal catalysts described in the reviewed literature. (C) 2010 Elsevier B.V. All rights reserved.