Ag nanoparticles-coated macroporous SiO2, structure was fabricated by a novel approach in which at first Ag nanoparticles were coated onto polystyrene (PS) spheres without a surfactant, then these Ag nanoparticles-coated PS beads (Ag/PS) were self-assembled by sedimentation-aggregation with tetraethyl orthosilicate (TEOS), and finally Ag nanoparticles-coated macroporous silica (Ag/SiO2) was obtained after removal of the PS cores. The heat-treatment temperature and the gelation time were investigated to optimize the microstructural morphology, thermal decomposition of organic materials, matrix wall thickness and densification behavior. The three dimensionally assembled Ag/SiO2 had 200 nm uniform macropores and a high specific surface area of 142 m(2) g(-1). The XRD, FE-SEM, EDX, BET and optical absorbance analysis indicated that the exactly three-dimensional structure of the template had been imprinted in the final samples and the walls of the macroporous SiO2 were coated uniformly with Ag nanoparticles. (c) 2006 Elsevier B.V. All rights reserved.