Reaction of tris{[}6-(2-hydroxymethyl)pyridylmethyl]amine, tpa(OH)(3), with (VOSO4)-O-IV center dot 5H(2)O resulted in an unexpected redox reaction producing {[}(VLH)-L-III]{[}(VLH2)-L-III]{[}PF6](3)center dot 1.5H(2)O (where H3L is bis(2-hydroxymethylpyridyl)(2-carboxypyridylmethyl)amine). This reaction is interesting in the light of the ability of ascidians to accumulate V-III by reduction of V-V from sea water. It also provides additional proof to the susceptibility of pyridylmethylamines to oxidation by certain metal ions.