Aqueous reactions of V2O5 or VCl3 in the presence of the physiological citric acid and hydrogen peroxide, in a pH specific fashion, afforded a new vanadium(V)-peroxo-citrate material isolated in a pure crystalline form. Elemental analysis pointed to the molecular formulation (NH4)(6)[(V2O2)-O-V(O-2)(2)(C6H4O7)(2)].4.5H(2)O (1). Complex 1 was further characterized by UV-vis, FT-IR, and X-ray crystallography. Compound 1 crystallizes in the monoclinic space group C2/c with a = 12.391(5) Angstrom, b = 15.737(7) Angstrom, c = 17.102(7) Angstrom, beta = 110.84(1)degrees, V = 3117(1) Angstrom(3), and Z = 4. The structure of the anionic assembly consists of a planar (V2O2)-O-V core with two fully deprotonated citrates bound to it through the central carboxylate and alkoxide moieties as well as one of the terminal carboxylate groups. The presence of one peroxide group attached to each vanadium(V) renders the geometry around each metal center pentagonal bipyramidal. Key structural and spectroscopic features of I correlate with those seen in the peroxo congener and low-pH analogue (NH4)(2)[(V2O2)-O-V(O-2)(2)(C6H6O7)(2)].2H(2)O (3), in which all terminal carboxylate groups are protonated. In solution, simple pH-dependent transformation of 1 to 3 attests to their participation in the requisite speciation and potentiates the presence of other similar peroxo analogues not yet isolated and characterized. The reactivity of 1 through transformation reactions, yielding a plethora of well-characterized species, establishes a linkage among various species with the same or different vanadium oxidation states. Collectively, the data reflect soluble forms of vanadium with peroxide and citrate that contribute to the requisite pH-dependent distribution of that metal ion and likely influence biological processes.