In this study, we conveniently obtained Ag(0)-polymer nanocomposites by reacting AgNO, with commercial poly(vinyl acetate) (PVAc) in the absence of a special reducing agent. The formation of Ag(0) metal was detected after formic acid (HCOOH) was added to a PVAc-AgNO3 complex system, and some of the acetate groups of the PVAc backbone were hydrolyzed to form hydroxyl groups (OH) under the catalytic effect of the reduced Ag(0) metal. Here, the structure of the partially hydrolyzed PVAc backbone was represented as PVOH-PVAc. X-ray diffraction spectra showed that the Ag(0) metal generated in this method was in the form of Ag crystals. The structure of the Ag(0)-polymer was analyzed by H-1-NMR and C-13-NMR spectroscopy. The micellization of the Ag(0)-polymer was also investigated by the addition of an inducing solvent to the formic acid solution of Ag(0)-polymer. The image showed that the morphology of the Ag micelles in the H2O-induced solvent was a Ag corona with a Ag shell, and that in the p-xylene induced solvent showed a Ag cluster core structure.