The interaction of the silver chemical vapor deposition precursor (1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedionato)(trimethylphosphine)silver(I), [(fod)AgP(CH3)(3)], with a polyurethane surface has been investigated with reflection-absorption infrared spectroscopy (RAIRS), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). The RAIR spectra show a decrease of the intensity of both polyurethane C=O and N-H vibrational bands at 90, 300, and 340 K. This suggests that a specific interaction occurs between [(fod)Ag(PMe3)] and polyurethane carbonyl groups at the surface, leading to the displacement of [P(CH3)(3)]. After exposure of polyurethane to the Ag complex at room temperature and above, XPS shows the presence only of Ag, F, and O, indicating displacement of [P(CH3)(3)] groups. The exposure of the adsorbed (fod)Ag-polyurethane complex to formaldehyde [HCHO] leads to additional deposition of silver and to the formation and the desorption of [1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedione], [fodH], from the polyurethane surface. AFM indicates that the silver is present in the form of clusters. Taken together, these data demonstrate the feasibility of low-temperature CVD of silver on organic polymer substrates.