Size-controlled immobilization of metal nano-clusters onto particles or nanoparticles is achieved using a polyol process. Polyol processing makes it possible to use thiol groups as a chemical protocol to functionalize the surface of particles, such as silica and polystyrene nanoparticles. Metal nano-clusters, such as silver, gold, platinum and palladium, nucleate and grow on the surface of the particles. The metal nano-clusters may be synthesized in a one-pot process from metal salts, nitrates, nitrites, sulfates, sulfites and the like. Any source of metal ions compatible with the polyol suspension and selected particles may be used. The size of immobilized metal nano-clusters may be controlled by additions of a poly(vinylpyrrolidone) or other polymer capable of regulating the metal ion reduction and nucleation process and by controlling concentration of metal ions, the nucleation and/or growth temperatures, and processing time.