Photocatalytic oxygenation of benzene to phenol occurs under visible-light irradiation of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) in an oxygen-saturated acetonitrile solution of benzene and tertbutyl nitrite. The photocatalytic reaction is initiated by photoinduced electron transfer from benzene to the triplet excited state of DDQ.