The combination system of CeO2-catalyzed carboxylation and 2-cyanopyridine hydration (CeO2 + 2-cyanopyridine system) is effective for the direct synthesis of organic carbonates from CO2 and alcohols. This catalyst system can be applied to various alcohols to afford the corresponding carbonates in high alcohol-based yields. The hydration of 2-cyanopyridine over CeO2 rapidly proceeds under the low concentration of water, which can remove the water from the reaction media. Since the reaction is limited by the chemical equilibrium, the removal of water remarkably shifts the chemical equilibrium to the carbonate side, leading to high carbonate yields. In addition, 2-picolinamide that is produced by hydration of 2-cyanopyridine forms an intramolecular hydrogen bonding between H atom of the amide group and N atom of the pyridine ring, which weakens the adsorption of 2-picolinamide on CeO2 by reduction of the acidity. The reaction mechanism of DMC formation in CeO2 + 2-cyanopyridine system is also proposed. (C) 2014 Elsevier Inc. All rights reserved.