Well-known vanadium(IV)- and vanadium(V)-citrate complexes have been employed in transformations involving vanadium redox as well as nonredox processes. The employed complexes include K-2[V2O4(C6H6O7)(2)].H2O, K-4[V2O4(C6H5O7)(2)]degrees5.6H(2)O, K-2[V2O2(O-2)(2)(C6H6O7)(2)].2H(2)O, K-4[V2O2(C6H4O7)(2)].6H(2)O, K-3[V2O2(C6H4O7)(C6H5O7)].7H(2)O, (NH4)(4)[V2O2(C6H4O7)(2)].2H(2)O, and (NH4)(6)[V2O4(C6H4O7)(2)].6H(2)O. Reactions toward hydrogen peroxide at different vanadium(IV,V):H2O2 ratios were crucial in delineating the routes leading to the interconversion of the various species. Equally important thermal transformations were critical in showing the linkage between pairs of dinuclear vanadium-citrate peroxo as well as nonperoxo complexes, for which the important vanadium(V)-assisted oxidative decarboxylation, leading to reduction of vanadium(V) to vanadium(IV), seemed to be a plausible pathway in place for all the cases examined. FT-IR spectroscopy and X-ray crystallography were instrumental in the identification of the arising products of all investigated reactions. Collectively, the data support the existence of chemical links between different and various structural forms of dinuclear vanadium(IV,V)-citrate complexes in aqueous media. Furthermore, in corroboration of past studies, the examined interconversions lend credence to the notion that the involved species are active participants in the respective aqueous distributions of the metal ion in the presence of the physiological ligand citrate. The concomitant significance of structure-specific species relating to soluble and potentially bioavailable forms of vanadium is mentioned.