In the present research account, three new ternary hybrid vanadium-peroxido-betaine compounds were synthesized. The first one has formulation K2[(VO)2(O2)4{(CH3)3NCH2CO2)}]•H2O. The second material is a ternary complex with a molecular formula Na2[V2(O2)4O2L2], L = Me3N(+)-CH2-COO(-). The third species is also a ternary compound with a molecular formula (NH4)2[(VO)2(O2)4{(CH3)3NCH2CO2)}]•0.75 H2O. The latter two materials have a similar structure. In all three compounds, vanadium occurs in the fully oxidized form of +5 and the yellow color of the crystals indicates the presence of more than one peroxide ligand bound to it. Confirmation of that contention came from X-ray crystallographic work, which projects the dinuclear character of the new species and its coordination environment. pH appears to be a major factor in the synthetic process leading to the isolation of the crystalline materials.