The reaction of [Ru(arene)Cl(2)](2) (arene = benzene, p-cymene) with [X(2)W(22)O(74)(OH)(2)](12-) (X = Sb(III), Bi(III)) in buffer medium resulted in four organo-ruthenium supported heteropolytungstates, [Sb(2)W(20)O(70)(RuC(6)H(6))(2)](10-) (1), [Bi(2)W(20)O(70)(RuC(6)H(6))(2)](10-) (2), [Sb(2)W(20)O(70)(RuC(10)H(14))(2)](10-) (3), and [Bi(2)W(20)O(70)(RuC(10)H(14))(2)](10-) (4), which have been characterized in solution by multinuclear ((183)W, (13)C, (1)H) NMR, UV-vis spectroscopy, electrochemistry, and in the solid state by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and elemental analysis. Polyanions 1, 2, and 4 crystallize in the triclinic system, space group P1 with the following unit cell parameters: K(5)Na(5)[Sb(2)W(20)O(70)(RuC(6)H(6))(2)] x 22 H(2)O (KNa-1), a = 12.1625(2) A, b = 13.1677(2) A, c = 16.0141(3) A, alpha = 78.9201(7) degrees, beta = 74.4442(8) degrees, gamma = 78.9019(8) degrees, and Z = 1; Cs(2)Na(8)[Bi(2)W(20)O(70)(RuC(6)H(6))(2)] x 30 H(2)O (CsNa-2), a = 11.6353(7) A, b = 13.3638(7) A, c = 16.7067(8) A, alpha = 79.568(2) degrees, beta = 71.103(2) degrees, gamma = 80.331(2) degrees, and Z = 1; Na(10)[Bi(2)W(20)O(70)(RuC(10)H(14))(2)].35H(2)O (Na-4), a = 15.7376(12) A, b = 15.9806(13) A, c = 24.2909(19) A, alpha = 92.109(4) degrees, beta = 101.354(4) degrees, gamma = 97.365(3) degrees, and Z = 2. Polyanions 1-4 consist of two (L)Ru(2+) (L = benzene or p-cymene) units linked to a [X(2)W(20)O(70)](14-) (X = Sb(III), Bi(III)) fragment via Ru-O(W) bonds resulting in an assembly with idealized C(2h) symmetry. Polyanions 1-4 are stable in solution as indicated by the expected (183)W, (13)C, and (1)H NMR spectra. The electrochemistry of 1-4 is described by considering the reduction and the oxidation processes. The nature of the arene in Ru(arene) has practically no influence on the formal potentials of the W-centers, which are more sensitive to the Sb or Bi hetero atoms. The results suggest that the respective Sb- and Bi derivatives have very different pK(a) values, with the reduced form of 1 being the most basic, thus permitting the observation of two well-developed voltammetric waves at pH 6. In contrast, the identity of the arene influences the oxidation processes, thus permitting to distinguish them. A strong electrocatalytic water oxidation peak is observed that is more positive than the one corresponding to the Ru(arene) oxidation process. Also a stepwise oxidation of the Ru(benzene) group could be observed at pH 3. The catalytic efficiency, on the other hand, of 1-4 toward the oxidation of n-hexadecane and p-xylene illustrated the effect of ruthenium substitution on the polyanion catalytic performance.