Branched dextran-graft-polyacrylamide copolymers (D-g-PAAn) with different number of PAA-grafts have been synthesized for further conversion them to polyelectrolytes dextran-graft-(polyacrylamide-co-polyacrylic acid). It is shown that D-g-PAAn internal structure in water solution is more compact in comparison with linear polyacrylamide and depends upon the distance between PAA grafts. The branched polyelectrolytes are obtained by alkaline hydrolysis of synthesized D-g-PAAn samples. The conversion of nonionic polymers to partial anionic form depends upon the macromolecular internal structure of D-g-PAAn. The degree of transformation of amide groups to carboxylate ones is higher for branched copolymers than for linear PAA at the same condition. The synthesized branched copolymers are shown to be perspective as flocculation agents and the matrices for synthesis of the stable Ag nanosystems.