Effects of pore structures of alumina on the catalytic performance of copper catalysts for CO2 hydrogenation were investigated. Copper-loaded hierarchical meso-macroporous alumina (Cu/HAl) catalyst exhibited no significant difference in terms of CO2 conversion with copper-loaded unimodal mesoporous alumina (Cu/UAl) catalyst. However, the selectivity to methanol and dimethyl ether of the Cu/HAl catalyst was much higher than that of the Cu/UAl catalyst. This was attributed to the presence of macropores which diminished the occurrence of side reaction by the shortening the mesopores diffusion path length. The Cu/HAl catalyst also exhibited much higher stability than the Cu/UAl catalyst due to the fast diffusion of water out from the catalyst pellets, alleviating the oxidation of metallic copper to CuO. (C) 2015 Elsevier Ltd. All rights reserved.