A OD vanadium borophosphate [Co(en)(3)](2)[V3P3BO19][H2PO4] . 4H(2)O (1) and two 1 D vanadium oxides (Co(en)(3)][V3O9] . H2O (2) and [Co(dien)(2)][V3O9].H2O (3) have been synthesized hydrothermaily from the reaction mixture of V2O5-H3PO4-H3BO3-COCl2-R-H2O at 110 degreesC (R: en or dien). The complex cations Co(en)(3)(3+) and Co(dien)(2)(3+) are cooperatively organized in the reaction medium to play a structure-directing role in the formation of the inorganic clusters and chains. The structures are determined by single-crystal X-ray diffraction analysis and further characterized by X-ray powder diffraction, ICP, and TG analyses. The structure of 1 contains isolated [V3P3BO19](5-) cluster anions, H2PO4- anions, racemic Co(en)(3)(3+) cations, and H2O molecules, which form a complex H-bond network. 2 and 3 both contain chains of corner-sharing VO4 tetrahedra running along the 21 screw axis. The complex cations located in the interchain region interact with the chains through H-bonds. 2 is crystallized in an enantiomorphic space group and only one enantiomer of Co(en)(3)(3+) is involved in the structure. Crystal data: 1, monoclinic, C2/c, a = 32.8492(14) Angstrom, b = 11.9601(3) Angstrom, c = 22.6001(7) Angstrom, beta = 108.9630(8)degrees, Z = 8; 2, orthorhombic, P2(1)2(1)2(1), a = 8.1587(16) Angstrom, b = 12.675(3) Angstrom, c = 18.046(4) Angstrom, Z = 4; 3, monoclinic, P2(1)/c, a = 16.1663(10) Angstrom, b = 8.7028(3) Angstrom, c = 13.9773(5) Angstrom, = 103.1340(18)degrees, Z = 4.