Catalytic hydrogenation of CO2 to valuable chemicals or liquid fuels is a promising way to recycle and utilize CO2. In the present study, elementary steps leading to the formation of formate and CO, two important intermediates in CO2 hydrogenation on Ni/gamma-Al2O3, have been explored using the density functional theory (DFT) slab calculations. Two systems: Ni-4 cluster supported on the dry gamma-Al2O3(1 1 0) surface, D(Ni-4), and on the hydroxylated gamma-Al2O3(1 1 0) surface, H(Ni-4), have been used to model Ni/gamma-Al2O3. On D(Ni-4), the reaction energy and activation barrier for formate formation are -0.23 eV and 1.25 eV, respectively, whereas those for CO formation are -0.48 eV and 2.13 eV, respectively. As such, formate formation is preferred kinetically while CO formation is more facile thermodynamically. On H(Ni-4), the reaction energy and activation barrier for formate formation are -0.36 eV and 2.32 eV, respectively, whereas those for CO formation are -0.67 eV and 0.69 eV, respectively. Consequently. CO formation becomes more favorable both kinetically and thermodynamically. These results indicate that hydroxylation of the gamma-Al2O3 support alters the pathway, and ultimately, the selectivity of CO2 hydrogenation on Ni/gamma-Al2O3. This conclusion supports the fact that varying the reaction environment such as water partial pressure is often used to improve the selectivity of a reaction. (C) 2010 Elsevier Inc. All rights reserved.