Characterization of polystyrene on etched silver substrates has been carried out using ion scattering (ISS) and X-ray photoelectron spectroscopy (XPS). The results have been used to describe the variation of time-of-flight secondary-ion yield (TOF-SIMS) for polystyrene as a function of coverage. It was determined that the TOF-SIMS secondary-ion yield increases with surface coverage up to ca. 0.50 and then drastically decreases for coverages greater than 0.55. XPS results also indicate that polystyrene forms a multilayer structure, a minimum of 5 layers thick on the Ag surface over the concentration range investigated (1 mu g/mL to 50 mg/mL).