The reaction mechanisms for HCOOH oxidation on a series of PtAu(111) alloy surfaces in the aqueous solution phase are investigated by density functional theory calculations. It is found that the dehydrogenation pathway of HCOOH oxidation occurs through the formation of formate with a barrier of 16.8 kcal mol(-1) and requires at least one Pt atom on the surface. In contrast, the CO formation pathway proceeds through the dimerization with a barrier of 5.6 kcal mol(-1), for which at least three Pt atoms with a non-equilateral structure are required. The calculated average electrostatic potential, charge density difference, Bader charge and partial density of states all show obvious charge transfer from the alloy surface Pt atoms to HCOOH molecules, indicating that Pt sites are the reaction active center. Different ensemble of Pt sites on PtAu(111) surfaces can have significant impact on the catalysis performance for HCOOH oxidation. The non-equilateral Pt site upon PtAu(111) should be avoided to eliminate CO poisoning effect on Pt-based catalysts. (C) 2014 Elsevier B.V. All rights reserved.