The charge-neutral antimonatopolyoxovanadium (IV) cluster [(V16Sb4O42)-Sb-IV-O-III(H2O){(VO)-O-IV(C6H14N2)(2)}(4)] center dot 10H(2)O center dot C6H14N2 was obtained under solvothermal conditions. The central cluster fragment, [(V16Sb4O42)-Sb-IV-O-III], is a derivative of the [V18O42] archetype and is formed by replacing two VO5 polyhedra by two Sb2O5 units. The {V20Sb4} structure expands the {V16Sb4} motif by the addition of four square-pyramidal, terminal VO(1,2-diaminocyclohexane)(2) groups. At low temperatures, the magnetic ground state is characterized by four independent S = 1/2 sites.