Ag nanoparticles-coated macroporous SiO 2 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/SiO 2 ) 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/SiO 2 had 200nm uniform macropores and a high specific surface area of 142m 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 SiO 2 were coated uniformly with Ag nanoparticles.