Results of the investigations carried out on the optical properties of silver particulate films deposited at a rate of 0.4 nm/s on softened polystyrene and poly(4-vinylpyridine) (P4VP) blends held at 455 K are reported. Under the conditions of deposition, a sub-surface particulate structure is expected. It had been shown earlier that the morphology of the sub-surface particulate structure is dependent on polymer-metal interaction. In the present studies, an inert polymer like polystyrene (PS) is blended with an interacting polymer P4VP. The optical studies on the silver particulate films deposited on softened blends of PS/P4VP have been carried out. The results show a shift in plasmon resonance to higher wavelength with increasing P4VP concentration of the blends in comparison to that of the films deposited on pure PS. An X-ray photoelectron spectroscopy study at two different electron take off angles indicates the formation of subsurface particulate structures for films deposited on blends.