The inline coupling of capillary electrophoresis (CE) to Taylor dispersion analysis was used for the characterization of polyelectrolyte complexes. The charge stoichiometry and the hydrodynamic radii of the two polyelectrolyte constituents were determined in a fully automated single run using standard commercial CE apparatus with a single detection point. The proposed methodology utilizes unusual high ionic strength (1.3 M) background electrolyte to obtain the dissociation and electrophoretic separation of polyelectrolyte constituents. Such highly saline conditions in combination with neutrally coated capillary were found to avoid any polyelectrolyte interactions onto the capillary surface. This innovative methodology should greatly contribute to simplify and accelerate the characterization of polyelectrolyte complexes or polyplexes.