The silver nanoparticles (Ag NPs) have been immobilized onto silica microspheres through the adsorption and subsequent reduction of Ag(+) ions on the surfaces of the silica microspheres. The neat silica microspheres that acted as the core materials were prepared through sol-gel processing; their surfaces were then functionalized using 3-mercaptopropyltri-methoxysilane (MPTMS). The major aims of this study were to immobilize differently sized Ag particles onto the silica microspheres and to understand the mechanism of formation of the Ag nano-coatings through the self-assembly/adsorption behavior of Ag NPs/Ag(+) ions on the silica spheres. The obtained Ag NP/silica microsphere conglomerates were characterized by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and energy-dispersive spectroscopy (EDS). Their electromagnetic wave shielding effectiveness were also tested and studied. The average particle size of the obtained Ag NPs on the silica microsphere was found that could be controllable (from 2.9 to 51.5 nm) by adjusting the ratio of MPTMS/TEOS and the amount of AgNO(3).