Synthesis of ethanol by hydrogenation of carbon dioxide has been investigated by developing the novel composite catalysts. The three different kinds of elementary reaction functions for ethanol synthesis were undertaken. The catalytic functions are partial reduction of CO2 to CO, C-C bond formation, and -OH group insertion. For this purpose, supported Rh catalyst, Fe-based modified Fisher-Tropsch catalyst, and Cu-based modified methanol synthesis catalyst were combined by different ways. As a result, high space-time yields of ethanol as high as 0.8-0.9 kg/l h were obtained.