The adsorption of a series of six cationic polyelectrolytes onto a gold surface was monitored via a quartz crystal microbalance with dissipation (QCM-D). The series of polyelectrolytes were chemically similar but differing in the ratio of two randomly ordered constituent monomers, one of which was charged, the other neutral. Thus the series of polyelectrolytes differed systematically in their charge densities, ranging from a high charge density (100% of monomers charged) to a low charge density (1% charged). It was determined that high charge density polyelectrolytes adsorbed in a relatively flat and rigid layer, while the low charge density polyelectrolyte, as expected, adsorbed in a much more extended structure that coupled strongly to the bulk solvent. By comparison to X-ray photoelectron spectroscopy results, we have also calculated the relative solvent mass hydrodynamically coupled to the adsorbed polymer, which ranges from almost 80% solvent for the 1% charged case down to close to zero for the 100% charged case. Since the QCM-D results are measured relative to uncoated gold in aqueous solution, the latter results should be interpreted as showing that the amount of water hydrodynamically coupled to gold and that coupled to gold coated with the 100% charged polyelectrolyte is very similar. It is believed that this systematic study on the effect of polyelectrolyte structure on the measured dissipation change in the QCM-D may serve as a first guide when inferring structural and viscoelastic information based solely on the QCM-D technique for other similar systems. In addition, a preliminary study on the ability of one polymer to replace another preadsorbed polymer layer was conducted that showed that a steric layer was able to prevent the adsorption of a thermodynamically more favorable polymer. In the reverse case, greater exchange was possible.