Preparation for graphene (GE)-meso-macroporous SiO2 composite was studied, the composite was used as the support for Ru and the resulted catalyst was applied to the preferential oxidation of CO (COPROX) in H-2-rich gases. The composite was characterized by using techniques of SEM, TEM, XRD, TPR, N-2 adsorption/desorption and XPS. In the preparation, polystyrene foam and a tri-block copolymer of P123 were used as the template for the macropores and the mesopores, respectively. In addition to the macro and the meso pores, there are narrow slit-like pores with width of several nanometers between GE and SiO2. The highly dispersed Ru nanoparticle can be loaded on the surface of GE in the composite by impregnating. Thus prepared Ru/GE-SiO2 showed very good catalytic performance for CO-PROX, especially exhibited high activity at low temperature. The GE-SiO2 composite should possess the properties of both meso-macroporous oxides and graphene, and is a kind of new promising material, in which SiO2 can be replaced by other oxides. Crown Copyright (c) 2014 Published by Elsevier B.V. All rights reserved.