Colloidal Ag nanoparticles were formed by X-ray irradiation in the presence of a polymer. This new synthesis method is simple, rapid and leads to a high production yield. Compared to the citrate-reduced Ag colloidal, polymer-protected Ag nanoparticles are smaller in size and more stable-and therefore suitable for biomedical application-as verified by TEM observation, XAFS measurement and optical characterization. Ag nanoparticles so produced were also visualized in solution and in real time by a visible light microscope based on dark field light scattering. The color-derived size and distribution of Ag nanoparticles correlates well with the hydrodynamic size data.