Hydrogenation of CO2 to ethanol was carried out over Rh/SiO2 based catalysts. The main product over the unpromoted catalysts was methane. By adding various metal oxide promoters to the catalysts, CO2 conversion and selectivity to alcohols (methanol and ethanol) increased. Among the promoters, Li salts showed the most prominent effect on ethanol production. Reaction conditions were optimized for ethanol formation over Rh-Li/SiO2 catalysts. An ethanol selectivity of 15.5% and a CO2 conversion of 7.0% were obtained at P = 5 MPa and T = 513 K in a flow of H-2-CO2 premixed gas (H-2/CO2 = 3) with a flow-rate of 100 cm(3)/min. By in situ FT-IR analysis of the adsorbed species on the catalysts, the reaction was suggested to proceed via CO intermediate(s).