The liquid-phase catalytic oxidation of benzene to directly produce phenol was studied under microwave irradiation using FeCl3/γ-Al2O3 as the catalysts prepared by the microwave-impregnated method. The catalysts were characterized by XRD and N2 adsorption techniques. The results indicated that the performance of the catalysts was significantly affected by the amount of Fe(III) loaded onto the γ-Al2O3 and microwave irradiation time. The influence of the reaction conditions, such as reaction temperature, the amount of catalyst, amount of hydrogen peroxide on the yield of phenol was investigated under microwave irradiation. Coupled conventionally heated method gives phenol yield of 9.8 %, the FeCl3/γ-Al2O3 prepared by the microwave-impregnated method gives higher phenol yield of 15.2 % and selectivity of 100 % when irradiated with microwave energy.