Positively and negatively charged molecules, endothelia, and cells play important roles in biological salted aqueous media. This work aimed at studying artificial polyelectrolyte complexes in terms of formation and stability in the context of the increasing interest for the use of polyelectrolyte systems in drug delivery or as polyelectrolyte complexes or polyplexes for gene transfection. The effect of salt concentration on model polyelectrolyte complexes was studied both experimentally and from a theoretical viewpoint. The critical salt concentration at which phase separation appeared when multifunctional polyanions, namely poly(Llysine citramide) and poly(L-lysine citramide imide) were mixed with poly(L-lysine) showed that salt concentration, degree of polymerization and charge density conditioned the formation and the stability of corresponding polyelectrolyte complexes. Data agreed well with the trends indicated by the theoretical approach and they are discussed in comparison with the case of nonviral transfection using polyplexes.