3,4-dihydro-1,3-2H-benzoxazines as novel one-electron donators for silver(I) ion into nano-metallic silver was firstly found and reported. The silver formation from nano-spherical particles to coral-like and dendrite-like structures was presented. With respect to the characterization results, the feasible reaction mechanism of the silver formation was proposed as an electron donated from benzoxazine to silver(I) ion, resulting in a radical cationic species of benzoxazine and silver(0). Based on this reduction process, a new approach for nano-silver coating on various surfaces such as fumed silica (SiO2), titanium dioxide (TiO2), carbon black (CB), chitosan (CS) including plastic sheet (polycarbonate, PC) and pellet (polyvinyl alcohol, PVA), was also revealed. Besides the nano-silver coated products were applied as antimicrobials fillers for Staphylococcus aureus ATCC 25923, Bacillus subtilis ATCC 6633, Micrococcus luteus ATCC 9341, Escherichia coli ATCC 25922, Pseudomonas aeruginosa ATCC 2785 and Candida albicans ATCC 10231. (C) 2015 Elsevier B.V. All rights reserved.