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A novel nano-heterostructure of AgI/Bi2MoO6 photocatalyst was successfully synthesized via a facile depositionprecipitationmethod. The samples were systematically characterized by X-ray diffraction, scanning and transmission electron microscopy, X-ray photoemission spectroscopy, UV–Vis absorption spectroscopy, and photoluminescence spectra. While sole Bi2MoO6 or AgI showed poor activity toward photocatalytic rhodamine B degradation, the nano-heterostructure was found with superior performance. The AgI/Bi2MoO6 composite with an optimal content of 20 wt％ AgI exhibited the highest photocatalytic degradation rate. Rhodamine B was totally degraded within 75 min visible-light irradiation. Moreover, the hybrid photocatalyst also showed a fairly good stability for several-cycle reuse. This study indicates that the AgI/Bi2MoO6 nano-heterostructure can be used as an effective candidate for photocatalytic degradation of organic pollutants.