Аннотация:The reactions in the solutions of nonstoichiometric polyelectrolyte complexes and anionic surfactants were studied by the luminescence quenching technique, turbidimetric titration, and velocity sedimentation. It was shown for the first time that carboxyl-containing surfactants can compete successfully with polyanion in reactions of polycation addition. The composition of the products of this interaction, i.e., polymer-colloidal complexes, was studied and a scheme for competing reactions was proposed.