Carbon monoxide hydrogenation was studied over a γ-alumina-supported 1 wt.% Rh catalyst by means of kinetic and in situ-Infrared measurements. The study was carried out at 200-300ºC, 0 – 22.5 kPa H2 and 1 – 7.5 kPa CO. The in-situ FTIR scrutiny of catalyst surface shows that adsorbed CO* species and vacancies dominate the Rh surface, while no effect of H2 and H2O pressures on surface coverage was observed at the conditions studied. Kinetic data are consistent with a mechanism in which the C-O bond dissociation is assisted by a double H-addition while H2 dissociative adsorption, CO molecular adsorption and the HCO* formation are quasi-equilibrated steps. A two-parameter Langmuir-Hinshelwood rate expression is deduced for CH4 formation, in agreement with the proposed sequence of elementary steps and kinetic data. The effect of temperature on parameters α and KCO leads to an apparent activation energy of 82.3 kJ·mol-1, an average CO adsorption enthalpy of -14.1 kJ·mol-1 and an entropy change of -17.9 J·mol-1·K-1. In-situ FTIR experiments show a full coverage of Rh surface with adsorbed CO below 200ºC and this CO* coverage decreases as temperature increases in the range 200-300ºC; It is also observed that the heat of CO adsorption on Rh surface decreases with CO* coverage.