In this present work, three generations of dendrigraft poly(l-Lysine) (DGL) were studied regarding their ability to interact with linear poly (acrylamide-co-2-acrylamido-2-methyl-1-propanesulfonate) (PAMAMPS) of different chemical charge densities (30% and 100%). Frontal analysis continuous capillary electrophoresis (FACCE) was successfully applied to determine binding constants and binding stoichiometries. The effect of DGL generation on the interaction was evaluated for the first three generations (G2, G3, and G4) at different ionic strengths, and the effect of ligand topology (linear PLL vs. dendrigraft DGL) on binding parameters was evaluated. An increase of the biding site constants accompanied with a decrease of the DGL-PAMAMPS (n:1) stoichiometry was observed for increasing DGL generation. The logarithm of the global binding constants decreased linearly with the logarithm of the ionic strength. This double logarithmic representation allowed determining the extent of counter-ions released from the association of DGL molecules onto one PAMAMPS chain that was compared to the total entropic reservoir constituted by the total number of condensed counter-ions before the association.