A novel catalyst, [Mo2V2O9(bpy)(6)][PMo11VO40], was synthesized by the self-assembling of [PMo11VO40](4-) and [Mo2V2O9(bpy)(6)](4+) unit and characterized by elemental analyses, TG, IR, X-ray powder diffraction and X-ray single crystal diffraction. [Mo2V2O9(bpy)(6)][PMo11VO40] with multi-isolated active sites showed good catalytic activities for hydroxylation of benzene to phenol. A high yield of phenol (25.5%) with selectivity to phenol of 90.7% was obtained using H2O2 as oxidant. The catalyst can be recycled for 5 times while its structure was unchanged and its catalytic activity was maintained. (c) 2013 Elsevier B.V. All rights reserved.