Density Functional Theory was applied to investigate the hydrogenation of CO2 to HCOO or CO on Pt-4/gamma-Al2O3(110) catalyst. It was found that the formation of CO is preferred to that of HCOO, kinetically and thermodynamically, indicating that methane can be formed on the Pt-based catalysts preferably. Furthermore, rather low an activation barrier (0.34 eV) for the formation of trans-COOH species was found, compared with that on Pt(111) surface (0.59 eV), showing that the interface between Pt-4 cluster and gamma-Al2O3(110) slab promotes the hydrogenation of CO2. However, the activation barrier for the dissociation of cis-COOH species on the supported catalyst is 0.91 eV, which is much higher than that on pure metal surface (0.56 eV). An electronic transfer channel was found to reconcile the divergence. Our results indicate that Pt/gamma-Al2O3 should be a promising candidate for the catalytic hydrogenation of CO2 by adjusting the metal/support interface to balance the activation barriers for the formation of trans-COOH and the dissociation of cis-COOH species. (C) 2016 Elsevier B.V. All rights reserved.