The direct hydroxylation of benzene using molecular oxygen by atmospheric pulse DC corona discharge was investigated. The conversion of benzene increased with the increase of oxygen content and input voltage but the selectivity of phenol decreased due to the formation of polymerized products. The reactivity was also influenced by the kind and content of background inert gas. By using argon as background gas, we could get 2.2% of phenol yield at 60degreesC and 1 atm with energy consumption of 50 W. The strategy of reductive oxidation, which added hydrogen to the reactant, was not favorable to the phenol formation in this reaction system. The polymerized product showed the oligomeric character and the analysis of its chemical structure with FT-IR was presented.