We performed CO 2 hydrogenation over Li-promoted Rh ion-exchanged zeolite catalysts (Li/RhY). As the amount of added Li increased, the main product transformed from methane to CO. Simultaneously, we observed promotion of ethanol production, as well as methanol production. Moreover, when 1.8% of CO was mixed with the reactant gas, the selectivity for ethanol was increased to as high as 13% on Li/RhY (Li/Rh=10), but no influence was observed on Rh ion-exchanged zeolite catalyst (RhY). We studied the mechanism of the promotion effect of Li by means of in situ FT-IR observations. IR spectra of CO/CO 2 adsorption and those for subsequent TPR were observed. On RhY, CO 2 molecules were adsorbed as terminal CO species which were the same as those found in CO adsorption. However, on Li/RhY, a new peak appeared at 1618cm - 1 by CO 2 adsorption and relatively stable species were formed on Li/RhY (Li/Rh=10). The results indicate that the Li additives created a new reaction path on the catalyst surface, where CO 2 adsorption enhancement as well as stabilization of adsorbed CO species occurred.