First principle calculations are performed to study the interfacial photoelectric properties of Agn/Bi2WO6 (0 0 1) (n=1, 2, 3, 4) hybrid photocatalyst. The parallel adsorption of Ag cluster leads to more energetic favorable structures due to stronger interfacial interactions. The positive charged Ag cluster may act as excited electron traps and facilitate the electron-hole separation. In particular, hybridization between Ag 5s and 0 2p leads to the formation of isolated energy levels above the valence bands, and they become more dispersed with broader bandwidth with the increment of silver cluster size, which is responsible for the enhanced absorption in visible-light region. In the deep valence region, Ag 4d orbital turns more delocalized and hybrid with 0 2p states as the cluster size increases, which contributes to more covalent bond feature of Ag-O. Moreover, optical spectra demonstrate obvious red-shifts of the absorption edge with the increment of silver content, which enhances efficiently the visible-light photocatalytic activities of Bi2WO6 (0 0 1). The study provides insights into the enhanced photocatalyic mechanism of Ag/Bi2WO6 (0 0 1) and aids in the design of noble metal loaded visible-light plasmonic photocatalyst. (C) 2015 Elsevier B.V. All rights reserved.