Raman and infrared spectra of aqueous solutions of vanadates have been studied from pH 8 to > 14, and assignments are proposed for the vibrational frequencies of (VO4)3–, (HVO4)2–, (V2O7)4–, (HV2O7)3–, and (VO3)nn–. It appears that there is tetrahedral co-ordination of the vanadium in all these ions.