A method for in situ monitoring of surface and gas species utilizing separately the difference and sum reflectivity of two polarizations, normal and parallel to the surface, measured by polarization-modulation infrared reflection-absorption spectroscopy is presented. Surface and gas-phase spectra were separately but simultaneously obtained from the reflectivities. The technique is combined with modulation excitation spectroscopy to further enhance the sensitivity, and a small-volume cell was designed for this purpose. CO oxidation over a 40 nm Pt film on aluminum was investigated under moderate pressure (atmospheric pressure, 5% CO, and 5%–40% O2) at 373–433 K. The surface species involved in the oxidation process and the gas-phase species, both reactant (CO) and product (CO2), could be simultaneously monitored and analyzed quantitatively. In addition, the reflectivity change of the sample during the reaction was assigned to a near-surface bulk property change, that is, surface reconstruction to the oxide phase. Under an O2-rich atmosphere, two reactive phases, denoted as low- and high-activity phases, were identified. A large amount of atop CO was observed during the low-activity phase, while the adsorbed CO completely disappeared during the high-activity phase. The presence of an infrared-inactive CO2 precursor formed by the reaction between surface oxide and gaseous CO during the high-activity phase was inferred. The desorption of the CO2 precursor is facilitated under a CO-rich atmosphere, most likely, by surface reconstruction to metallic Pt and a competitive adsorption of CO on the surface.