We report the first structures of simple acetate complexes of vanadium(III) formed in aqueous solution. Paramagnetic H-1 NMR spectroscopy titration experiments indicate the formation of two major V(III)/acetate complexes in acidic aqueous solution for acetateN(III) <= 4, pD 3.50. A novel tetranuclear cluster and a trinuclear cluster have been characterized by X-ray diffraction studies. Mass spectrometry measurements show these clusters retain their integrity in solution.