CO dissociation on clean and hydrogen covered Nickel/Yttrium-Stabilized Zirconia (Ni/YSZ) with interface oxygen vacancy is studied using the first-principles method based on density functional theory. It is found that the CO can be trapped at the interface 0 vacancy and the trapped CO can dissociate to C and 0 with a much lower dissociation barrier as compared with that on the pure Ni (111) surface (1.74 vs 2.89 eV). When H atom precovers the Ni part, the H associated CO dissociation path (H + CO -> CHO, CHO -> CH + O) is preferred, while when H atom precovers at the YSZ part, the direct CO dissociation (CO -> C + O) is preferred. Overall, either the H at the Ni part or the YSZ part, the CO dissociations are both accelerated (0.90, 1.41 vs 1.74 eV). Therefore, we propose that the carbon deposition may form easily at the interface oxygen vacancy of triple phase boundary (TPB) and the precovered H atom can accelerate the CO dissociation, which offers new understanding on the carbon deposition of the Ni/YSZ anode of solid oxide fuel cell with the pure CO or CO and H-2 mixture as the fuel. (C) 2015 Elsevier B.V. All rights reserved.