The oxidation of oxovanadium(IV) complexes [(LVO)-O-IV] (L = tetradentate Schiff-base ligands such as N,N'-ethylenebis(salicylideneaminate)(2-) (salen) and N,N'-2,2-dimethylpropylenebis(salicylideneaminate)(2-) (salpn)) to [(LVO)-O-v](+), believed to be responsible for the voltammetric response near 0.6 V vs Ag/AgCl in CH2Cl2 in the presence of tetrabutylammonium tetrafluoroborate as a supporting electrolyte, is in fact coupled to a homogeneous process where [LVO](+) coordinates BF4- to form a neutral complex formulated as [LVOBF4]. The formation constants for [VO(salen)BF4] and [VO(salpn)BF4] are evaluated to be K-salen(-1) = 1.1 X 10(2) M-1 and K-saipn(-1) = 1.4 x 10 M-1, respectively. Crystal structure of [VO(salen)BF4] reveals that one of the fluorine atoms in BF4- is so close to the vanadium(V) atom as to be practically bound in the solid state.