In this paper, Cu2O/TiO2 composite porous microspheres were prepared in the absence of templates and additives by a simple hydrothermal method using Cu(CH3COO)(2)center dot H2O and (NH4)(2)TiF6 as precursors. The photocatalytic activity of the samples was evaluated by the photo-degradation of methylene blue (MB) aqueous solution under the visible-light illumination. To the best of our knowledge, this is the first report on the preparation and photocatalytic activity of Cu2O/TiO2 composite porous microspheres with a template-free hydrothermal method. This work may provide new insights into preparing other inorganic porous microspheres. (C) 2011 Elsevier B.V. All rights reserved.