Silver nanoparticles self-assembled on poly(4-vinylpyridine) modified surfaces were spin-coated with poly( methyl methacrylate), poly(butyl methacrylate) and polystyrene from anisole and toluene solutions. The polymers filled the space between the particles thereby providing stabilization of the assemblies against particle aggregation when dried or chemically modified. The polymers did not coat the top surface of the nanoparticles offering the chemical accessibility to the metal surface. This was confirmed by converting the stabilized nanoparticles into silver sulfide and gold clusters. Etching the nanoparticles resulted in crater-like polymeric structures with the cavities extending down to the underlying substrate. Electrochemical reduction of silver inside the craters was performed. The approach can be extended to other nanoparticle assemblies and polymers. (C) 2015 Elsevier B.V. All rights reserved.