Polyelectrolyte multilayers and layer-by-layer assemblies are susceptible to structural changes in response to ionic environment. By altering the salt type and ionic strength, structural changes can be induced by disruption of intrinsically bound ion pairs within the multilayer network via electrostatic screening. Notably, high salt concentrations have been used for the purposes of salt-annealing and self-healing of LbL assemblies with KBr, in particular, yielding a remarkably rapid response. However, to date, the structural and swelling effects of various monovalent ion species on the behavior of LbL assemblies remain unclear, including a quantitative view of ion content in the LbL assembly and thickness changes over a wide concentration window. Here, we investigate the effects of various concentrations of KBr (0 to 1.6 M) on the swelling and de-swelling of LbL assemblies formed from poly(diallyldimethylammonium) polycation (PDADMA) and poly(styrene sulfonate) polyanion (PSS) in 0.5 M NaCl using quartz-crystal microbalance with dissipation (QCM-D) monitoring as compared to KCl, NaBr, and NaCl. The ion content after salt exchange is quantified using neutron activation analysis (NAA). Our results demonstrate that Br- ions have a much greater effect on the structure of as-prepared thin films than Cl- at ionic strengths above assembly conditions, which is possibly caused by the more chaotropic nature of Br-. It is also found that the anion in general dominates the swelling response as compared to the cation because of the excess PDADMA in the multilayer. Four response regimes are identified that delineate swelling due to electrostatic repulsion, slight contraction, swelling due to doping, and film destruction as ionic strength increases. This understanding is critical if such materials are to be used in applications requiring submersion in chemically dynamic environments such as sensors, coatings on biomedical implants, and filtration membranes.