Only a few studies have so far focused on the addition of silver to SS316L alloys by conventional sintering methods. Unfortunately, the metallurgical process of silver-containing antimicrobial SS is greatly limited due to the extremely low solubility of silver in iron and its tendency to precipitate at the grain boundaries, resulting in an inhomogeneous distribution of the antimicrobial phase and loss of antimicrobial properties. In this work, we present a novel approach to fabricate antibacterial stainless steel 316L by functional polyethyleneimine-glutaraldehyde copolymer (PEI-co-GA/Ag catalyst) composites. PEI is a highly branched cationic polymer, which makes it exhibit very good adhesion on the surface of the substrate. Unlike the effect of the conventional silver mirror reaction, the introduction of functional polymers can effectively improve the adhesion and distribution of Ag particles on the surface of 316LSS. It can be seen from the SEM images that a large number of silver particles are retained and well dispersed in 316LSS after sintering. PEI-co-GA/Ag 316LSS exhibits excellent antimicrobial properties and does not release free silver ions to affect the surrounding environment. Furthermore, the probable mechanism for the influence of the functional composites on the enhancement of adhesion is also proposed. The formation of a large number of hydrogen bonds and van der Waals forces, as well as the negative zeta potential of the 316LSS surface, can effectively enable the formation of a tight attraction between the Cu layer and the surface of 316LSS. These results meet our expectations of designing passive antimicrobial properties on the contact surface of medical devices.