Transmetallation of the tetramine Schiff-base complex [Ba(H2L)(H2O)2][ClO4]2 with vanadium(III) trichloride, vanadyl(IV) sulfate trihydrate or vanadyl(IV) dichloride dihydrate gave [V2L(H2O)4][ClO4]2Cl21, [V2L(H2O)4][ClO4]4·H2O 2 and [V2L(H2O)4][SO4]2·H2O 3, respectively {H2L = 1,7,14,20-tetramethyl-2,6,15,19-tetraaza[7.7](2,6)pyridinophane-1,6,14,19-tetraene-4,17-diol}. Incorporation of two vandium(III) ions within the macrocyclic cavity also resulted from the template action of these oxovanadium(IV) salts upon 2,6-diacetylpyridine and 1,3-diaminopropan-2-ol in refluxing methanol. No evidence was obtained for any vanadium(IV)-containing species having been produced en route. Metathetical precipitation reactions of 3 with various barium salts led to the isolation of [V2L(H2O)4][X]4·nH2O species (X = Cl 4, SCN 5, NO36, or I 7, n= 2–8). These complexes exhibit reduced magnetic moments at 295 K. Variable-temperature magnetic susceptibility studies on representative powdered samples of 1 and 5 showed weak intramolecular antiferromagnetic coupling between the vanadium(III) centres (J=–20 and –25 cm–1, respectively) together with a smaller intermolecular contribution (θ=–2.0 and –3.7 cm–1, respectively). Cyclic voltammetric studies on acetonitrile solutions of 2 revealed two waves attributable to sequential one-electron metal-centred reduction processes to yield [V2L]3+ and [V2L]2+ species. No evidence was found for the existence of any VIV-containing species, through either electrochemical and /or chemical oxidation experiments.