In order to avoid damage to the substrate surface and environment pollution by the traditional electroless plating (ECP) pretreatment process, we have designed and fabricated Ag complexes based on multidentate ligands (SAAP) toward highefficient and facile ECP. The SAAP solution is a mixture of deionized water, alcohol, 3-aminopropyltriethoxysilane, and AgNO 3 . A strong force is established between hydrolyzed silane and Ag particles by means of Ag−N and Ag−O coordinated bonds. More importantly, it could coat on the different substrate surfaces by means of Ag complexes based on the SAAP structure using the rapid film-forming (dip-coating, brush-coating, and in situ filmforming) process which could be attributed to Si−OH and −NH 2 groups on the SAAP surface. As a result, octahedral Ag particles are evenly distributed on the substrate surface with excellent stability and ECP catalytic ability after SAAP film forming. The less stable HCHO is generated and then converted into H−COOH with charge transfer to Cu 2+ through Ag d-orbitals and vacant orbitals, which results in the reduction of Cu 2+ to Cu atoms around Ag particles in ECP-Cu solution. To be precise, an easy method to achieve surface metallization of polymers and inorganic materials via coating SAAP solution combined with ECP is achieved successfully. This work is helpful to promote ECP industrial development.