The ethanol synthesis from carbon dioxide on rhodium metal is reviewed. The control of Rh active site is important to inhibit the methane formation (complete reduction of CO2) and at the same time, to activate the carbon-carbon bond formation by the reaction of CHx with carbonyl derivative. A hypothesis of acetyl and acetate intermediates is described on the basis of study on single crystal Rh surface. As a potential ethanol synthesis catalyst, supported Rh/TiO2 catalyst was recently discovered promoted by selenium from inside the Rh metal sites.