Reactions of laser-ablated iron oxides with CO in excess argon are investigated by infrared adsorption spectroscopy and density functional theoretical calculations. The carbonyl iron oxides OFe(CO)(n) (n = 1-3) and O(2)Fe(CO)(m) (m = 1, 2) are generated during sample deposition or annealing, whereas CO(2) is greatly produced at the expense of these carbonyl iron oxides upon UV irradiation, showing the formation of intermediate carbonyl iron oxides in the oxidation of carbon monoxide to carbon dioxide. These intermediate carbonyl iron oxides are characterized on the basis of isotopic substitution, stepwise annealing, change of CO concentration and laser energy, and comparison with theoretical calculations. The overall agreement between the experimental and calculated vibrational frequencies, relative absorption intensities, and isotopic shifts supports the identification of these complexes from the matrix infrared spectra. The reaction pathways for the formation of the products are proposed based on the experimental and theoretical results presented.