A family of three discrete organoantimony(III)-functionalized heteropolyanions-[Na{2-(Me2HN+CH2)C6H4SbIII}AS(2)(III)W(19)O(67)(H2O)](10-) (1), [{2-(Me2HN+CH2)C6H4SbIII}(2)(As2W19O67)-W-IIII(H2O)](8-) (2), and [{2-(Me2HN+CH2)C6H4SbIII}{WO2(H2O)}{WO(H2O)}(2)(B-beta-(AsW8O30)-W-III)(B-alpha-(AsW9O33)-W-III)(2)](14-) (3)-have been prepared by one-pot reactions of the 19-tungstodiarsenate(III) precursor [(As2W19O67)-W-IIII(H2O)](14-) with 2-(Me2NCH2)C6H4SbCl2. The three novel polyanions crystallized as the hydrated mixed-alkali salts Cs3KNa6[Na{2(Me2HN+CH2)C6H4SbIII}(As2W19O67)-W-IIII(H2O)]center dot 43H(2)O (CsKNa-1), Rb2.5K5.5[{2(Me2HN+CH2)C6H4SbIII}(2)(As2W19O67)-W-IIII(H2O)]center dot 18H(2)O center dot Me2NCH2C6H5 (RbK-2), and Rb2.5K11.5[{2-(Me2HN+CH2)C6H4SbIII}WO2(H2O)}{WO(H2O)(2) (B-beta-(As2W8O30)-W-IIII)(B-alpha-(AsW9O33)-W-III)(2)]center dot 52H(2)O (Rbk-3), respectively. The number of incorporated {2-(Me2HN+CH2)C6H4SbIII} units could be tuned by careful control pseud. Bacillus subtilis of the experimental parameters. Polyanions 1 and 2 possess a dimeric sandwich-type topology, whereas 3 features a trimeric, wheel-shaped structure, representing the largest organoantimony-containing polyanion. All three compounds were fully characterized in the solid state via single-crystal Xray diffraction (XRD), infrared (IR) spectroscopy, and thermogravimetric analysis, and their aqueous solution stability was validated by ultraviolet-visible light (UV-vis) and multinuclear (H-1, C-13, and W-183) nuclear magnetic resonance (NMR) spectroscopy. Effective inhibition against six different types of bacteria was observed for 1 and 2, and we could extract a structure-bioactivity relationship for these polyanions.