Surface-enhanced Raman spectroscopy (SERS) in conjunction with mass spectroscopy (MS) has been utilized to investigate the adsorption and hydrogenation of carbon monoxide on polycrystalline rhodium surfaces. The SERS-active Rh substrates were prepared by electrodeposition of ultrathin films on electrochemically roughened gold and display remarkably robust SERS activity over a wide range of temperatures (up to 400 °C) and pressures (here up to 1 atm). The SER spectra reveal that CO adsorbed primarily on atop sites (νRh - C = 470 cm-1) and desorbed by about 250−300 °C under all gas-phase conditions examined. Partial dissociation of the CO adlayer, however, was obtained at temperatures as low as 100 °C, most likely facilitated by the large number of steps and kinks present on these roughened surfaces. This was evidenced by a partial removal of CO at temperatures (ca 100 °C) well below those expected for thermal desorption (200−250 °C) and supported by the observed formation of surface carbonate (665 cm-1) under these conditions. The CO dissociation, however, is hampered at lower temperatures (<200 °C) when gas-phase H2 and/or CO are present, most likely due to blocking of site ensembles necessary for decomposition to proceed. Interestingly, heating a CO adlayer in pure H2 resulted in the formation of an adsorbed oxygen species (νRh - O = 295 cm-1) at temperatures above 250 °C. The CO hydrogenation reaction was examined over a wide range of gas-phase conditions (H2:CO = 99:1 to 4:1 at 1 atm), with methane being the only hydrocarbon product detectable with MS. In addition to the presence of adsorbed CO observed up to 250 °C under all H2/CO reaction ratios, the adsorbed oxygen species noted above was detected at higher temperatures (>250 °C) when a low percentage of CO (≤1%) in the feed reactant stream was used. The influence of the adsorbed species on the overall methanation rates is discussed in light of these findings. Utilizing the seconds time-scale resolution of SERS, the exchange between gas-phase and adsorbed CO was also studied. The results of such transient 13CO/12CO exchange experiments reveal that this desorption pathway is weakly activated (≈1 kcal mol-1), first order with respect to CO coverage, yet independent of CO partial pressure in the regime studied (8−760 Torr). This contrasts the first-order pressure dependence for much lower CO partial pressures (≤10-5 Torr) reported earlier in the literature. A rate law and mechanism are proposed which account for these differences and rationalize the observed behavior.