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The functional materials based on silver nanoparticles (NPs) are widely used in biotechnology and medicine. It is shown that maleic acid copolymers (CMA) are effective stabilizers of silver NPs. These copolymers have the following advantages as compared to other polymer stabilizers of NPs: biocompatibility and biodegradability, commercial availability, regular chemical structure of polymer chain, solubility in water in a wide range of pH values, and possibility to vary the hydrophobic-hydrophilic balance of CMA. In the present study, we have studied in detail the structure formation in the solutions of CMA with ethylene or N-vinylpyrrolidone, the process of formation of CMA-silver salt, and the structure of CMA/Ag0 sols and nanocomposites. It is shown by dynamic and static light scattering that diluted solutions of CMA, CMA-Ag+ salt and CMA/Ag0 hydrosols were partially aggregated. pH range of micellization in CMA solutions depends of comonomer hydrophobosity. The complexation of Ag+ ions takes place inside individual macromolecules as well as inside polymer aggregates that results in a formation of unimolecular core-shell micelles and micellar clusters having a polyelectrolyte shell and Ag NPs embedded in a polymer network as a core. According to TEM data silver NPs stabilized by CMA have sizes of 1.5–3.5 nm. CMA/Ag0 hydrosols and nanocomposites could be used in practice as antiseptic agents. Antifungal activity of sols against plant pathogen F. Oxisporum has been demonstrated.