A mononuclear dialkoxo-bound monooxo-vanadium(V) complex, VO(acetylacetosalicylhydrazone)(OEt) 1, was synthesized and structurally characterized. In a chloroform solution, complex 1 exists in two forms. The major species is a monomeric form, as in the solid-state structure, and the minor species converts to the monomeric form in the presence of a small amount of ethanol.