Hydroxylation of benzene to phenol is one of the challenging topics for the transition from C—H bonds to C—O bonds. In this paper, the research progress of the reaction mechanism of benzene hydroxylation catalyzed by vanadium-based catalysts to phenol is discussed. Taking vanadium activity center as the main line, the paper focuses on the detailed analysis and summary of three aspects: free radical, non-radical mechanisms and dual-catalysis mechanism, and covers the nature of the high efficiency of such catalysts and the importance of catalytic microenvironment. Because such catalytic systems and catalytic mechanisms can provide theoretical guidance for solving scientific problems such as inert C—H bond on benzene rings and deep oxidation of phenol. Therefore, it is necessary to focus on phenol synthesis methods that coexist with economy and safety, and at the same time rely on the existing catalytic reaction mechanism to develop more stable and high-performance catalysts to promote the original innovation of abundant hydrocarbon organic compound resource utilization in China.