Synthesis of stable silver colloids was achieved using nitrogen-containing polymers acting simultaneously as a reducing and stabilizer agent. The polymers polyethyleneimine (PEI), polyvinylpyrrolidone (PVP) and poly(2-vinyl pyridine)--poly(ethylene oxide) (PEO--P2VP) were used in the procedures. The influence of the surface chemistry and chemical nature of the stabilizer on the cytotoxicity and antimicrobial properties have been evaluated. The produced nanomaterials were found to be non-toxic up to the highest evaluated concentration (1.00 ppm). Nevertheless, at this very low concentration, the AgNPs stabilized by PVP and PEO--P2VP were found to be remarkable biocides against bacteria and fungus. On the other hand, we have surprisingly evidenced negligible antimicrobial activity of AgNPs stabilized by positively charged PEI although both (AgNPs and PEI) materials separately are known for their antimicrobial activity as also evidenced in the current investigation. The evidence is claimed to be related to the blocking of Ag kinetic release. Accordingly, the antimicrobial effect of nano-sized silver colloids largely depends on the chemical nature of the polymer coating. Possibly, the outstanding colloid stabilization provided by polyethyleneimine slows down Ag release thereby hampering its biological activity whereas the poorer stabilization and good ionic transport property of PVP and PEO--P2VP allows much faster ion release and cell damage.