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 ...