The photocatalytic hydroxylation of benzene to phenol is an important reaction for the synthesis of fine chemicals and pharmaceuticals. However, the development of efficient and selective photocatalysts for this reaction remains a challenge. Here, a highly active and selective Fe‐MOF/2D‐montmorillonite (Fe‐MOF/MMT) photocatalyst was prepared via an in‐situ method for the hydroxylation of benzene to phenol under the visible light irradiation. The Fe‐MOF/MMT composite exhibited excellent photocatalytic performance, with phenol yield of 30.3% and benzene selectivity of 96.5% within 4 hours. The high activity and selectivity of the Fe‐MOF/MMT photocatalyst were attributed to the synergistic effect between the Fe‐MOF and MMT, as well as the unique 2D structure of MMT, which facilitated charge separation and transfer. The Fe‐MOF/MMT composite also showed good stability and re‐used without significant decrease of activity. This study demonstrated that the potential of Fe‐MOF/MMT as a highly efficient and selective photocatalyst for the hydroxylation of benzene to phenol and provided an insight into the design of advanced photocatalysts for sustainable chemical synthesis.