Two coordination polymers based on vanadium-substituted Keggin polyoxotungstophosphates as bridging ligands, {[Ni(4,4′-bipy)1.5(OH)(H2O)]2[H3PW10V2O40]}·4H2O (4,4′-bpy = 4,4′-bipyridine) 1 and {[Ni(dpa)2][Ni(dpa)(H2O)3]2[PW9V3O40]}·4H2O (dpa = 2,2′-dipyridylamine) 2, have been obtained by hydrothermal reactions and characterized by elemental analysis, IR, XRD, TGA and single-crystal X-ray Diffraction analysis. Compound 1 is a 2D layered structure built from 1D infinite zigzag {Ni2(4,4′-bipy)3(OH)2(H2O)2} n 2+ chains bridged via [H3PW10V2O40]2− anions. Compound 2 exhibits a one-dimensional chain-like structure constructed from [Ni(dpa)2]2+ fragments bridged via bis-supported Keggin polyoxoanions [Ni(dpa)(H2O)3]2[PW9V3O40]2−. The two examples demonstrate that vanadium-substituted Keggin polyoxometalates have greater coordination capability.