The reactivity of a Lu2O3-promoted Rh/Al2O3 catalyst in the CO/H2 reaction is reported. Methane, heavier hydrocarbons, methanol, and ethanol are obtained. In situ DRIFTS has been employed to record the infrared spectra under the actual reaction conditions. The structure of the observed COads DRIFTS bands has been resolved into its components. The production of oxygenates (methanol and ethanol) has been correlated with the results of the deconvolution calculation. Specific sites for the production of methanol and ethanol in the CO/H2 reaction over a Rh,Lu2O3/Al2O3 catalyst are proposed.