The formation of polyelectrolyte complexes is known to depend on many factors, especially pH, temperature, and ionic strength, as well as acid-base properties and mixing conditions. In an approach aimed at by-passing the complexity of blood, the formation and the stability of complexes between oppositely charged polymers were studied in salted media (0.15N NaCl and 0.13 M, pH 7.4 PBS) at room temperature. Different molar masses of poly(L-lysine) were reacted with polyanions with different chemical structures and charge densities, namely: poly(acrylic acid), poly(L-lysine citramide), poly(L-lysine citramide imide), and poly(malic acid). A stepwise protocol was used to investigate the fractionation phenomena reported previously. After each addition, the precipitate was separated and analyzed. The polyanion macromolecules were fractionated according to their structure; no significant fractionation was observed for the polycation. The NaCl concentration, required to destabilize the complexes in the isolated fractions, was found to depend on the polycation molar mass and to vary linearly with log(polyanion Mw). Based on these data, the possible fate of polycationic species, and of polycation-based polyelectrolytic complex, when injected into blood, are addressed.