A novel catalyst, [Mo 2 V 2 O 9 (bpy) 6 ][PMo 1 1 VO 4 0 ], was synthesized by the self-assembling of [PMo 1 1 VO 4 0 ] 4 - and [Mo 2 V 2 O 9 (bpy) 6 ] 4 + unit and characterized by elemental analyses, TG, IR, X-ray powder diffraction and X-ray single crystal diffraction. [Mo 2 V 2 O 9 (bpy) 6 ][PMo 1 1 VO 4 0 ] 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 H 2 O 2 as oxidant. The catalyst can be recycled for 5 times while its structure was unchanged and its catalytic activity was maintained.