Water-soluble complexes formed by pyrenyl-tagged poly(methacrylate) anion with cationic DAB-dendr-(NH2)(x) of five generations, x = 4, 8, 16, 32, and 64 were prepared and studied. The ability of the dendrimers to quench the pyrenyl fluorescence was used to monitor formation/dissociation of the complexes by fluorescence quenching technique. In salt-free solutions, dissociation of the complexes occurred in highly acidic and highly alkaline media independently on the dendrimer generation, whereas stability of the complexes against destruction by added salt (NaCl) enhanced markedly with x increase. Phase separations were dependent on pH and charged ratio of the components, but independent of a dendrimer generation. By contrast, in water-salt solutions the generation had a profound impact on phase diagram manifested by a considerable extension of a heterogeneity region as x increased. These findings strongly suggest that the complexes obey the main regularities ascertained for polyelectrolyte complexes of oppositely charged polyions. The revealed possibility of preparing negatively charged and positively charged complexes with controllable stability and solubility demonstrates potentialities of Astramol dendrimers for design self-assembled and self-adjusted systems attractive for biotechnological and biomedical applications.