In order to realize the convenient process of metalization on different materials and make electroless plating more efficient and fast, a multi-dentate ligand Ag complex (MLAg) was synthesized, which components include deionized water, 3-aminopropyl triethoxysilane, polyvinyl alcohol, and silver nitrate. It is worth noting that because the surface of MLAg contains a large number of -NH₂ and -OH groups, it can be coated on different substrate surfaces through a process of rapid film formation (in situ film generation, brush coating, and dip coating) with a special structure (silver nanoparticles/polymer brush (Ag/PB) structure). Of note, we introduced polyvinyl alcohol as a structural optimization scheme to improve the structure of the Ag/PB interface (enhancing the Ag adsorption strength and electronic structure), which has a beneficial inhibitory effect on the growth of Ag grains. Of note, the MLAg/Ag interfacial force is a strong bond cooperation by means of covalent bond. The results show that the polyhedral Ag particles are composed of triangular (111) and square (100) crystal planes, and are evenly distributed on the surface of the substrate with outstanding film-forming performance, speed and catalytic ability. In the Cu chemical plating solution, HCHO exhibits an unstable free state and transforms into H-COOH, Ag d-orbitals and open orbitals donate their charge to Cu²⁺, enabling reduction to Cu atom, and thereby deposition on substrate surface. Furthermore, the excellent film-forming and catalytic capacity of as-fabricated MLAg make it suitable for a pre-treated material with a metallized surface.