Selective hydroxylation of benzene is a felicitous strategy for the production of phenol that is deemed to be an alternative to conventional processes. Thus, the development of a durable and highly efficient catalyst for the selective hydroxylation of benzene should be a key topic. In this work, FeOCl was prepared by a chemical vapor transition method and characterized using various techniques including XRD, TEM, Raman spectroscopy, N2 adsorption–desorption, DLS, and TGA. The prepared FeOCl was applied as a heterogeneous catalyst in benzene hydroxylation, and the reaction conditions were optimized. The acquired data manifested that FeOCl has shown superiority over the other reported catalysts utilized in benzene hydroxylation. The superiority of FeOCl is attributed to the facile self-redox potential of FeOCl and its remarkable ability for the production of an overwhelming amount of hydroxyl radicals in a short period of time. The catalyst recovery and reuse test showed that FeOCl is able to endure the har...