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A novel transition metal ion bridging bis(diphosphopentamolybdates) has been synthesized and characterized by elemental analysis, IR spectrum, UV spectrum and single-crystal X-ray diffraction. The single-crystal structure analysis shows that the compound consists of seven charge-compensating 2,2-biimidazole cations (BIIM = 2,2-biimidazole) and one dumbbell-like [Mn(H2O)4(P2Mo5O23)2]10- heteropolyanion which is construeted by two [P2Mo5O23]6- clusters bridged through one [Mn(H2O)4]2+ cation.