A density functional theory (DFT) based method in conjunction with the projector augmented wave and pseudopotential methods have been applied to investigate the adsorption of Pt-4 and Pt3Ni on the anatase TiO2 (1 0 1) surface. Two stable Pt3Ni adsorptions with considerable adsorption energies on the anatase TiO2 (1 0 1) surface were identified. Analysis of the partial density (PDOS) of states and Bader charge suggest that the electronic structure of Pt is modified by Ni due to the electron transfer from Ni to Pt atoms in the Pt3Ni clusters. The 2cO (3cO)-PtNi-5cTi conformation of the adsorbed Pt3Ni on the anatase TiO2 (1 0 1) surface provides a more feasible model for electron injection through the Pt3Ni/TiO2 interface. The reactivity of Pt3Ni/TiO2 is superior to Pt-4/TiO2 and effectively manifests itself in the eased decomposition of O-H bonds derived by methanol and alleviative CO adsorption. (C) 2014 Elsevier B.V. All rights reserved.