Direct synthesis of ethanol from syngas derived from coal, natural gas, or biomass is one of the most promising routes for renewable energy production. In this work, Ce-promoted highly-dispersed Rh catalyst on TiO2 support was prepared by the deposition-precipitation method, which exhibits largely enhanced catalytic activity and selectivity for ethanol production from syngas. XRD and TEM reveal a high dispersion of Rh nanoparticles (similar to 1 nm) on the surface of TiO2 support by the introduction of CeO2. It was found that the relative content of Rh and CeO2 imposes significant influence on the catalytic behavior, and the sample of 1 wt% Rh-1 wt% CeO2/TiO2 exhibits the highest CO conversion (32 %) and the largest ethanol selectivity (33 %) under the conditions of 573 K, 3 MPa, H-2:CO = 2:1. H-2-TPR and XPS results confirm a gradually enhanced electron interaction between Rh and CeO2 with the increase of Ce content; CO-TPD further reveals that the Rh-CeO2 interaction generates a new adsorption site for CO, accounting for the improved selectivity towards ethanol. Therefore, this work provides a facile and effective method for the preparation of Rh-CeO2/TiO2 catalysts with high catalytic behavior, which can be potentially used in syngas conversion to ethanol.