Abstract <p>The structures of small silver clusters (Ag, Ag₂, Ag₃) and their interaction with dioxidine oligomers (Dx, Dx₂, Dx₃, Dx₄) are calculated using the density functional method in the B3LYP5 parameterization. Tendencies in the geometric structure and the energy of the “metallic cluster—dioxidine oligomer” interaction are estimated as functions of the degree of ligand and metal aggregation. It is shown that as the number of dioxidine molecules in the oligomer ligand increases, the energy of binding of the Ag_<i>n</i> cluster with the dioxidine NO group does not change essentially (for <i>m</i> ≥ 2 in Dx_<i>m</i>). This fact makes it possible to take into account the contribution of the Ag_<i>n</i>–NO bonds to the total dioxodine oligomer stabilization energy in a rather simple linear way. In addition, for all our studied dioxidine oligomers, a stable increase in the Ag_<i>n</i>–Dx_<i>m</i> interaction energy is observed as the number of silver atoms in the Ag_<i>n</i> cluster is increased. The largest binding energy exists for the Ag₃–Dx₄ system (15.1 kcal/mol). Thus, the interaction of relatively large silver clusters with dioxidine oligomers can have a significant influence when their hybrid nanocomposites form.</p>