Polyelectrolyte multilayers (PEMUs) are ultrathin membranes made by alternating adsorption of oppositely charged polyelectrolytes on substrates. Although PEMUs have shown exceptional selectivity for certain ion-filtering applications, they usually contain an excess of one of the polyelectrolytes due to the history- and condition-dependent mode of PEMU assembly. This excess charge provides fixed sites for ion exchange, enhancing the concentration of oppositely charged ions. Thus, the ion-permselective properties of PEMUs cannot be compared unless they are assembled under identical conditions. This work demonstrates the enhanced permeability of PEMUs as-made from poly(diallyldimethylammonium) (PDADMA), and poly(styrene sulfonate) (PSS) to ferricyanide as an example of an anion. Annealing by NaCl followed by pairing of excess PDADMA with additional PSS produces an almost stoichiometric film that better reflects the intrinsic transport properties of PEMUs. This pairing, observed in real time using electrochemical methods, occurs at the PEMU/solution interface under countercurrent transport of PSS from solution and excess PDADMA paired with a counterion, termed PDADMA*, from the PEMU bulk. A quantitative comparison of PSS and PDADMA* diffusion reveals the conditions under which PEMU assembly depends on PSS molecular weight and concentration.