The preparation of silver particulate films on softened polystyrene (PS) substrates and their characterisation using Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS) and optical absorption spectroscopy is reported in this paper. Silver films of 150 nm thickness were vacuum deposited onto PS coated glass substrates held at temperatures in the range 415-475 K at different deposition rates of 3 to 12 Angstrom/s. SEM studies indicate that films deposited at 415 K are close to a semicontinuous structure and the structure is discontinuous at higher temperatures. The film morphology is strongly dependent on the deposition rate at any given substrate temperature. The film agglomeration increases with increasing rate of deposition. In the XPS studies, considerable attenuation of the signal corresponding to silver is observed at lower electron take of angles (ETOAs). This indicates that Ag is formed beneath the PS surface. Optical absorption studies showed an interesting red shift of the plasmon resonance wavelength for lower deposition rates again indicating that a sub-surface particulate structure is formed at lower deposition rates. These results are consistent with reported observations.