Reactions of laser-ablated silver atoms with carbon monoxide molecules in solid argon and neon have been investigated using matrix-isolation IR spectroscopy. Small silver cluster carbonyls, (AgCO)(2) and AgnCO (n = 2-4), as well as mononuclear silver carbonyls, Ag(CO)(2) and Ag(CO)(3), are generated upon sample annealing in the argon experiments and are characterized on the basis of the isotopic substitution, the CO concentration change, and the comparison with theoretical predictions. However, these polynuclear carbonyls are absent from the neon experiments. Density functional theory calculations have been performed on these silver carbonyls and the corresponding ligand-free silver clusters, which support the identification of these silver carbonyls from the matrix IRspectrum. A terminal CO has been found in the most stable structures of (AgCO)(2), Ag2CO, Ag3CO, and Ag4CO. Furthermore, a plausible reaction mechanism has been proposed to account for the formation of the (AgCO)(2) and AgnCO (n = 2-4) molecules.