How to cite this paper: Pandey, P.P. (2015) Preparation and Characterization of Subsurface Silver Particulate Films on Polymer Blends of Polystyrene/Poly(2-vinylpyridine)/Poly(vinylpyrollidone)/Poly(4-vinylpyridine). Soft Nanoscience Letters, 5, 3-11. http://dx.Abstract Silver particulate thin films on softened polymer blends of Polystyrene (PS)/Poly(2-vinyl pyridine) (P2VP), PS/Poly(4-vinylpyridine) (P4VP), and Poly(vinylpyrollidone) (PVP)/P4VP at a rate of 0.4 nm/s held at a temperature of 457 K in vacuum of 8 × 10 −6 Torr by evaporation are deposited. These silver films were characterized by their electrical behavior, optical properties and Scanning electron microscopy (SEM). Silver films deposited on softened PS, and PVP give rise to a very high room temperature resistance approaching that of the substrate resistance due to the formation of a highly agglomerated structure. On the other hand, silver films on softened P2VP and P4VP give rise to a room temperature resistance in the range of tens to a few hundred MΩ/ which is desirable for device applications. Silver films on the composites of PS/P2VP, PS/P4VP and PVP/P4VP show resistances at room temperature. The optical and plasmonic response of Ag nanoparticles onto thin layers of blends shows encapsulation of nanoparticles. The electrical properties and SEM of silver nanoparticles on the thin layers of polymer blends indicate the formation of much smaller, narrower dispersion and wide size distribution.