The first peroxidovanadium trimer was prepared in the form of its tetrabutylammonium salt, (NBu4)3[V3O3(O2)6]·2H2O. Its X-ray structure analysis revealed a unique cyclic structure of the [V3O3(O2)6](3-) ion incorporating the yet unobserved μ3-η(2):η(1):η(1) coordination mode of one of its peroxido ligands. While relatively stable in nonaqueous solvents, the [V3O3(O2)6](3-) ion quickly decomposes in diluted aqueous solutions. A higher vanadium concentration or a higher CH3CN content in the mixed CH3CN/H2O solvent facilitates the formation of oligomers [V2O2(O2)4(H2O)](2-) and [V3O3(O2)6](3-). (51)V NMR investigations indicated that the trinuclear species is incorporated in vanadium-catalyzed oxidations in the presence of H2O2.