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The interaction of star-shaped poly(acrylic acid) with a linear strong cationic polyelectrolyte, exhaustively quaternized poly(4-vinylpyridine), in aqueous solutions was examined. It was demonstrated that water-soluble interpolyelectrolyte complexes with poly(acrylic acid) stars playing a lyophilizing part can be formed in such mixtures if the certain conditions are met, the characteristics of the formed complex particles are determined by the number of arms of the star-shaped poly(acrylic acid) and by the degree of polymerization of the cationic polyelectrolyte.