Herein, a novel open-framework vanadoborate, (H(2)en)(4)H-2[V12B18O54(OH)(6)(H2O)]center dot 11H(2)O (1, en = ethylenediamine), was hydrothermally synthesized and structurally characterized. The framework was constructed by discrete [V12B18O54(OH)(6)(H2O)](10-) polyanion clusters with H(2)en(2+) as counterions. An extended network of hydrogen bonds among polyanions, cations, and crystal water molecules links the structure in three dimensions. These structural features endow the present vanadoborate with unique proton conduction properties. This material shows a high proton conductivity of 1.87 x 10(-4) S cm(-1) at 333 K under the condition of 100% relative humidity, and the activation energy was estimated to be 0.38 eV.