Phenol is one of the most important chemicals in industry, and the world production exceeds 7.2 megatons per year. Industrially, phenol has been produced from benzene by the threestep cumene process, which is not only energy consuming but also less efficient. The process is known for its very low yields ( % 5 % based on the amount of benzene initially used) and for the large amounts of by-products such as acetone and amethylstyrene. Direct phenol synthesis from benzene is an alternative way to overcome these problems, and O 2 , [1-4] H 2 O 2 , [5, 6] N 2 O, [7-14] H 2 + O 2 , [15, 16] air/CO, [17] and O 2 /H 2 O [18] have been used as oxidants. The liquid-phase oxidation reactions of benzene with molecular oxygen in batch closed reactors have been reported to proceed over an ironheteropolyacid catalyst in the presence of excess catalyst and over a CuO/Al 2 O 3 catalyst with ascorbic acid as a reducing agent; however, the yield of phenol is very low. [1, 2] A Cu/ZSM-5 catalyst showed a maximum phenol selectivity of 60 % with a yield of 1.2 % at 673 K. [3] Despite good performances with N 2 O and H 2 O 2 as oxidants, no economically and environmentally favorable catalytic systems for the selective oxidation of benzene with O 2 to give phenol have been discovered to date because of the difficulties associated with the activation of molecular oxygen. The direct synthesis of phenol with molecular oxygen is thus still regarded as one of the 10 most difficult challenges for catalysis, [19-21] and the development of highly selective catalysts for this reaction is of great interest. Rhenium, which can adopt several oxidation states, provides unique catalytic performances in re-forming of petroleum feedstocks, alkene metathesis, selective oxidation of methanol to formaldehyde, and ammoxidation of