First-principles calculations based on density functional theory (DFT) have been used to investigate the reaction mechanism of dry methane reforming on Ni(111). The most energetically favorable adsorption configurations of the species involved in this process are identified and the transition states for all the possible elementary steps are explored by the dimer method. Then, the related thermodynamic properties at 973.15 K are calculated by including the zero-point energy correction, thermal energy correction and entropic effect. It is found that CO(2) dissociates via a direct pathway to produce CO and O dominantly, and atomic O is revealed to be the primary oxidant of CH(x) intermediates. Based on this information, two dominant reaction pathways are constructed as both the CH and C oxidation are found to be likely. The reaction network begins with the dissociation of CO(2) and CH(4), and then the generated CH and C are oxidized by atomic O to produce CHO and CO, followed by the CHO decomposition to finally generate CO and H(2). As for these two reaction pathways, the oxidation step is predicted to determine the overall reaction rate under the current investigated conditions, while the CH(4) dissociation is found to be the rate-limiting step at lower temperatures. (C) 2009 Elsevier B.V. All rights reserved.