The dimeric, sandwich-type tungstophosphate [{PhSbOH}(3)(A-alpha-PW9O34)(2)](9-) (1) has idealized D-3h symmetry and represents the first organoantimony-containing polyoxometalate. Polyanion 1 was synthesized in an aqueous, acidic medium via three different routes and was fully characterized in the solid state by X-ray diffraction, IR, and thermogravimetric analysis and in solution by multinuclear NMR (H-1, C-13, P-31, and W-183).