A novel plasmonic photocatalysts of Ag/AgCl-Bi2MoO6 was successfully synthesized via a simple and mild wet-chemical process. The physical and photophysical properties of the as-prepared Ag/AgCl-Bi2MoO6 samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), Ultraviolet-visible diffuse reflection spectroscopy (DRS), electron spin resonance (ESR), photoluminescence emission spectra (PL) and surface photovoltage spectroscopy (SPV). The interaction between Ag/AgCl and Bi2MoO6 has been investigated by X-ray photoelectron spectroscopy (XPS) analysis, and which is facile to the electron transfer between Ag/AgCl and Bi2MoO6 and result in the enhancing photocatalytic activity of Ag/AgCl-Bi2MoO6 composite. The photocatalytic experiments indicate that the Ag/AgCl species can efficiently promote the separation efficiency of photogenerated charge carriers in Bi2MoO6, and consequently improve the RhB photodegradation activity. The 20 wt% Ag/AgCl-Bi2MoO6 sample shows the highest photocatalytic activity, the degradation constant of 20 wt% Ag/AgCl-Bi2MoO6 was as high as 4 times to that of pure Bi2MoO6. A possible catalytic mechanism for Ag/AgCl-Bi2MoO6 is proposed, which can be attributed to the surface plasmon resonance (SPR) effect from Ag/AgCl species. (C) 2015 Elsevier B.V. All rights reserved.