Hydrothermal reactions of the V2O5/2,2':6':2 "-terpyridine/ZnO/H2O system under a variety of conditions yielded the organic-inorganic hybrid materials [V2O4(terpy)(2)](3)[V10O28]. 2H(2)O (VOXI-10), [VO2(terpy)][V4O10] (VOXI-11), and [V9O22(terpy)(3)] (VOXI-12). The structure of VOXI-10 consists of discrete binuclear cations [V2O4(terpy)(2)](2+) and one-dimensional chains [V10O28](6-), constructed of cyclic [V4O12](4-) clusters linked through {VO4} tetrahedra. In contrast, the structure of VOXI-11 exhibits discrete mononuclear cations [VO2(terpy)](1+) and a two-dimensional vanadium oxide network, [V4O10](1-) The structure of the oxide layer is constructed from ribbons of edge-sharing square pyramids; adjacent ribbons are connected through corner-sharing interactions into the two-dimensional architecture. VOXI-12 is also a network structure; however, in this case the terpy ligand is incorporated into the two-dimensional oxide network whose unique structure is constructed from cyclic [V6O18](6-) clusters and linear {V3O5(terpy)(3)} moieties of corner-sharing vanadium octahedra. The rings form chains through corner-sharing linkages; adjacent chains are connected through the trinuclear units. Crystal data: VOXI-10, C90H70N18O42V16, triclinic P (1) over bar, a = 12.2071(7) Angstrom, b = 13.8855(8) Angstrom, 16.9832(10) Angstrom, alpha = 69.584(1)degrees, beta = 71.204(1)degrees, gamma = 84.640(1)degrees, Z = 1; VOXI-11, C15H11N3O12V5, monoclinic, P2(1)/n, a = 7.7771(1) Angstrom, b = 10.3595(2) Angstrom, c = 25.715(4) Angstrom, beta = 92.286(1)degrees, Z = 4; VOXI-12, C45H33N9O22V9, monoclinic C2/c, a = 23.774(2) Angstrom, b = 9.4309(6) Angstrom, c = 25.380(2) Angstrom, beta = 112.047(1)degrees, Z = 4.