The hydrothermal reactions of CuSO₄·5H₂O, Na₃VO₄, 2,2′:6′:2″-terpyridine (terpy), and the appropriate organophosphonate ligand yield a series of materials of the Cu(II)-terpy/oxovanadium organophosphonate family. The complexes exhibit distinct structures spanning one-, two- and three-dimensions and exhibiting diverse oxovanadium building blocks. Thus, [{Cu(terpy)}(V₂O₄)(O₃PPh)(HO₃PPh)₂] (1) is one-dimensional and constructed from binuclear units of corner-sharing V(V) square pyramids. While [{Cu(terpy)}VO(O₃PCH₂PO₃)] (2), [{Cu(terpy)}₂(V₄O₁₀)(O₃PCH₂CH₂PO₃)] (3), and [{Cu(terpy)}(V₂O₄){O₃P(CH₂)₃PO₃}]·2.5H₂O (4·2.5H₂O) are similarly one-dimensional, the V/O structural components consist of isolated V(IV) square pyramids, tetranuclear V(V) units of three tetrahedra and one square pyramid in a corner-sharing arrangement, and isolated V(V) tetrahedra and square pyramids, respectively. The second propylenediphosphonate derivative, [{Cu(terpy)}(V₂O₄){O₃P(CH₂)₃PO₃}] (5) is three-dimensional and exhibits isolated V(V) tetrahedra as the vanadate component. The two-dimensional structure of [{Cu(terpy)(H₂O)}(V₃O₆){O₃P(CH₂)₄PO₃}] (6) is mixed valence with isolated V(IV) square pyramids and binuclear units of corner-sharing V(V) tetrahedra providing the V/O substructures.