A novel Ag2O/Ag3VO4/Ag4V2O7 photocatalyst was synthesized by adjusting the molar ratio of silver-vanadium (Ag-V) in a facile hydrothermal method to obtain multi-phase Ag2O/Ag3O4/Ag4V2O7 photocatalyst. The photocatalytic activity of the prepared samples was quantified by the degradation of Rhodamine B (RhB) model organic pollutant under visible light irradiation. Compared to pure Ag3VO4, Ag4V2O7 and P25 TiO2, respectively, the as-synthesized multi-phase Ag2O/Ag3VO4/Ag4V2O7 powders gave rise to a significantly higher photocatalytic activity, achieving up to 99% degradation of RhB in 2 h under visible light. This enhanced photocatalytic performance was attributed to the effect of the multiphase Ag2O/Ag3VO4/Ag4V2O7 photocatalyst and the surface plasmon resonance (SPR) of the incorporated metallic silver (Ag-0) nanoparticles (NPs) generated during the photocatalysis, as evidenced by post-use characterization, resulting in improved visible light absorption and electron-hole (e(-)-h(+)) separation. A mechanism was proposed for the photocatalytic degradation of RhB on the surface of Ag2O/Ag3VO4/Ag4V2O7. (C) 2015 Published by Elsevier Ltd.