The structures of small silver clusters (Agn, n = 1–3, n =13) and their complexes with 7-aminocholesterol (NCh) are calculated using density functional theory with B3LYP5 parameterization. The 7-aminocholesterol ligand has two active coordination centers: lone pairs on the N- and O-atoms. Trends in the geometric structure and interaction energy of the silver–7-aminocholesterol complexes are evaluated depending on the size of the metal cluster. It is found that coordination of the metal cluster to the nitrogen atom is preferable in all cases. The most stable complex is Ag3–NCh (Ag3–(N)–NCh), for which the dissociation energy reaches 15.6 kcal/mol.