[en] Highlights: • A highly active AgCl/Ag/AgFeO₂ photocatalyst was synthesized by a facile way. • Novel AgCl/Ag/AgFeO₂ composites exhibited high photocatalytic activity. • Z-scheme system hetrostructure mechanism was proposed. - Abstract: A new AgCl/Ag/AgFeO₂ composite was synthesized for the first time via a simple precipitation method. The very detailed characterizations were enforced in photocatalytic activity and stability. The photocatalytic performance was studied by the degradation of the rhodamine B (RhB, a cationic dye) under visible irradiation. The as-prepared AgCl/Ag/AgFeO₂ photocatalyst exhibited excellent photocatalytic activity and stability under the visible light region compared to pure AgCl and AgFeO₂. About 97.47% of RhB can be removed in 60 min by the optimized AgCl/Ag/AgFeO₂ composite, which was ∼2.26 and ∼10.83 times as fast as that pure AgCl and pure AgFeO₂. After three cycles visible light irradiation experiments found that degradation rate of RhB reached 76.35%, which was still higher than pure AgCl and AgFeO₂. The obviously enhanced photocatalytic activity of AgCl/Ag/AgFeO₂ composites can be attributed to the efficient separation of electron-hole pairs of the Z-scheme heterostructure between AgCl, Ag and AgFeO₂. In this study, we also found the superoxide radicals (·O₂⁻) was considered to be the dominant active radical in the degradation of dye.