Photocatalytic hydroxylation of phenol to dihydroxybenzenes (catechol and hydroquinone) in liquid phase over a novel heterogeneous photocatalyst TiO2/Reduced Graphene Oxide was investigated with the assistance of light irradiation at room temperature. The catalysts was characterized by, FT-IR, UV–vis DRS, SEM and XRD. The conversion of phenol could reach high up to 64.9%, with a total selectivity of 95% and the yield of 39.3%, 22.3% for catechol and hydroquinone, respectively.