We study specific features of the formation of structures of metal-filled composites based on the copolymers of 2-hydroxyethyl methacrylate with polyvinylpyrrolidone depending on the composition of the initial mixture and nature and content of the metal. It is discovered that metal powders introduced in a polymer play the role of additional points of cross-linking and promote the formation of more cross-linked structures. It is experimentally demonstrated that a polymer network formed in the presence of metal particles is characterized by different compositions in the interface layers on the surfaces of metal particle and in the bulk of the polymer. We also establish the relationship between the physicomechanical properties and structure of the obtained copolymers. We also reveal the possibility of controlled creation of cross-linked metal composites with predicted structure and a complex of properties.