The crystal structure determination of tris(vanadyl)-substituted tungstoantimonate(III) K-11 H[(VO)(3)(SbW9O33)(2)].27H(2)O reveals that the [(VO)(3)(SbW9O33)(2)](12-) anion contains three exterior VO2+ groups sandwiched by two alpha -B [SbW9O33](9-) ligands in V-IV...V-IV separation of 5.411(8)-5.464(8) Angstrom and is stabilized by equatorial three K+ ions triangle with virtual D-3h symmetry. An observable spin-exchange interaction between V-IV centers within the vanadyl coplanar triangle is demonstrated in terms of S = 1/2 and S = 3/2 states.