The core-shell structure of Ag@CeO2 was prepared by a novel and facile method, which was based on the photothermal effect of localized surface plasmon resonance (LSPR). Nanoparticles (NPs) of Ag were dispersed in a solution containing citric acid, ethylene glycol and cerium nitrate, then under irradiation, Ag NPs generated heat from LSPR and the heat-induced polymerization reaction in the interface between Ag and the sol resulted in cerium gel formation only on the surface of the Ag NPs. After calcination, Ag@CeO2 was successfully obtained, then Ag@CeO2/SiO2 was prepared by loading Ag@CeO2 on SiO2. The resultant catalyst exhibited favorable activity and stability for CO oxidation. The preparation method proposed here should be extendable to other composites with metallic cores and oxide shells in which the metallic nanoparticle possesses LSPR properties.