Binary polymer nanoparticles were synthesized by the reprecipitation of poly(4-vinylpyridine) in the presence of poly(diallyldimethylammonium chloride) and further used to make polymer-coated Ag nanoparticles. Polymer shells around Ag nanoparticles were formed by two methods: the reduction of Ag2O in the presence of the polymer nanoparticles and by mixing the polymer nanoparticles with already-made Ag nanoparticles. The resulting nanoparticles were coated with layers of the two polymers with the hydrophilic polymer on the outside providing their stability in water. The exposure of the polymer-coated Ag nanoparticles to unmodified Ag nanoparticles resulted in spontaneous self-assembly due to the electrostatic attraction. The polymer-coated nanoparticles and the nanoparticle assemblies were characterized by UV-vis, surface-enhanced Raman scattering spectroscopy, and transmission electron microscopy.