Novel high efficient photocatalyst is the key for photocatalytic hydrogen generation from water splitting. In this study, a novel hierarchical CuO/ZnO "corn-like" architecture was designed and synthesized via a combination of hydrothermal and photodeposition method. The as-prepared nanostructured materials was shown to effectively generate hydrogen in the mixture of methanol and water (v/v = 1:10). This is because the hierarchical CuO/ZnO "corn-like" architecture: 1) greatly enhances the light utilization rate due to its special architecture, 2) enlarges the specific surface area, providing more reaction sites and promoting mass transfer, 3) promotes the photogenerated electrons transfer from ZnO to CuO, achieving the anti-recombination effect of electrons and holes, and 4) avoids the photocorrosion of ZnO to improve the stability of ZnO as a catalyst during water splitting. Moreover, the novel hierarchical CuO/ZnO "corn-like" architecture is easily recovered for reuse. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.