The syntheses of five mixed ligand vanadium(III) phosphate/phosphonate complexes are described : dinuclear I, [LVCl{mu-(Pho)(2)Po-2}]2; II, [LVCl{mu-Ph(2)PO(2)}](2); and III, [LVCl{mu-PhP(H)O-2}](2); along with mononuclear IV, [LV{(PhO)(2)POS}(2)DMF]; and V, [LV{(PhO)(2)PO2}](2) . H2O where L = hydrotris(pyrazolyl)borate. X-ray crystal structure analysis of I, II, IV, and V gave the following parameters : I, C12H10B2Cl2N12O8P2V2, P1, a = 9.949(4)Angstrom, b=11.732(4) Angstrom, c=12.729(3) Angstrom, alpha=110.37(1)degrees, beta=106.78(1)gamma, gamma=104.36(1)degrees, Z=1, V=1228.8(7) Angstrom(3); II, C16H98B2Cl10N12O4P2V2, P1, a=11.801(2) Angstrom, b=12.086(1) Angstrom, c=12.955(2) Angstrom, alpha=81.99(1)degrees, beta=65.51(1)degrees, gamma=62.60(1)degrees, Z=1, V=1491.1(5) Angstrom(3); IV, C36H37BN7O7P2S2V, P1, a=11.003(2) Angstrom, b=11.816(2) Angstrom, c=17.167(5) Angstrom, alpha=98.68(2)degrees, beta=101.81(2)degrees gamma=102.59(2)degrees, Z=2, V=2087.0(6) Angstrom(3); V, C69.5H65B2N15O8P4V2, C2/C, a=12.360(2) Angstrom, b=26.362(4) Angstrom, c=23.254(2) Angstrom, beta=91.24(8)degrees, Z=4, V=7575(2) Angstrom(3). Magnetic measurements indicate little or no interaction between the V(III) ions in II but a modest antiferromagnetic coupling in I. These complexes should be good models for the possible modes of bonding between V(III) and biological phosphates such as DMA as well as provide insight into one of the common structural motifs present in vanadium(III) phosphate solid state materials.