V-HMS catalysts with different vanadium content have been prepared by co-synthesis method using dodecylamine as template. The isolated VO4 species are successfully incorporated into the framework of HMS for the samples with low vanadium content. The effect of various reaction conditions on the hydroxylation of benzene to phenol with H2O2 as oxidant in aqueous acetic acid solvent was investigated where the yield of phenol achieves 11.1% under the optimized condition.