A Ag/Ag₃PO₄/Bi₂MoO₆ hybrid was successfully prepared for the first time via an in situ precipitation method. The as-prepared Ag/Ag₃PO₄/Bi₂MoO₆ hybrid included Ag₃PO₄ nanoparticles (NPs) as well as Ag NPs assembling on the surface of Bi₂MoO₆ nanosheets. Under visible light irradiation (λ > 420 nm), the Ag/Ag₃PO₄/Bi₂MoO₆ hybrid photocatalyst degraded rhodamine B (Rh B) efficiently and showed much higher photocatalytic activity than pure Ag₃PO₄, Bi₂MoO₆, Ag/Ag₃PO₄, Ag/Bi₂MoO₆, or Ag₃PO₄/Bi₂MoO₆. It was elucidated that the excellent photocatalytic performance of Ag/Ag₃PO₄/Bi₂MoO₆ for the degradation of Rh B under visible light could be ascribed to the efficient separation of photogenerated electrons and holes through the Z-scheme system composed of Ag₃PO₄, Ag and Bi₂MoO₆, in which Ag NPs acted as the charge transmission-bridge. The quenching effects of different scavengers illustrated that O₂˙⁻ and h⁺ played the major role in Rh B degradation.