AlPO4 was synthesized by ionic liquid and aluminium isopropoxide, which was employed as carrier to support V2O5 for synthesizing the highly active catalysts of benzene hydroxylation. Physicochemical properties of catalysts were characterized by XRD, SEM, TEM, Mapping, FT-IR, XPS and N2 adsorption/desorption. And the catalytic performance of vanadium-based catalysts in the hydroxylation of benzene were investigated. Catalyst with 16% (based on the total mass of V2O5 and AlPO4, the same below) vanadium oxide loading would own the most and evenly distributed V4+ active centers, the acidic microenvironment that fitted the reaction. Under the following conditions: catalyst dosage 0.2 g, mass fraction 30% hydrogen peroxide 12.5 mL, benzene 4 mL, acetonitrile 15 mL, reaction temperature 70 ℃ and reaction time 7 h, the conversion of benzene was 53.4% and the selectivity of phenol was 98.4%. Based on the analysis of characterization and performance evaluation, it was concluded that the reaction mechanism might be mainly nucleophilic oxidation catalytic mechanism, supplemented by free radical mechanism.