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Results of the investigations carried out on particulate silver films, deposited at a rate of 0.4 nm s-1 on poly(4-vinylpyridine) coated substrates held at temperatures in the range 440-490 K in a vacuum of 8 × 10-6 Torr are reported in this paper. A morphological study by scanning electron microscopy and x-ray diffraction was further confirmed by optical absorption studies. The shift in the plasmon resonance towards longer wavelength is ascribed to polymer-metal particle interactions. Electrical resistances immediately after deposition and at room temperature show a regular dependence on the thickness for the films in the temperature range studied. The films deposited at lower substrate temperatures show a lower negative temperature coefficient of resistance when compared to films deposited at higher substrate temperatures. X-ray photoelectron spectroscopy studies indicate the formation of a sub-surface particulate structure at higher substrate temperatures.