AgI/MIL‐53(Fe) composites were fabricated through a simple solution method, and their photocatalytic activities on Rhodamine B (RhB) degradation were investigated. The results demonstrated that the introduction of AgI into the MIL‐53(Fe) was beneficial to the enhanced visible light response. Under visible light irradiation, almost 100 % RhB was bleached over AgI/MIL‐53(Fe) composites after 180 min. The promising photocatalytic performance was ascribed to three points: the existence of AgI helped to generate easily the electrons and holes in the composites; an intimate interfacial contact between MIL‐53 (Fe) and AgI offered the path for the charge carries transport; MIL‐53 (Fe) could fast transfer the excited electrons due to its inherent nature. Thus, these results were responsible for the effective inhibition of charge carrier recombination, resulting in an improved photocatalytic activity. [ABSTRACT FROM AUTHOR]