We demonstrate for the first time that the superlacunary polyanion [H2P4W24O94](22-) reacts with electrophiles. One-pot reaction of this precursor polyanion with dimethyltin dichloride in aqueous acidic medium results in the hybrid organic-inorganic [{Sn(CH3)(2)}(4)(H2P4W24O92)(2)](28-) (1). Single-crystal X-ray analysis was carried out on K17L11[{Sn(CH3)(2)}(4)(H2P4W24O92)(2)]center dot 51H(2)O (1a), which crystallizes in the tetragonal system, space group P4(2)/nmc, a = b = 21.5112(17) and c = 27.171(3) angstrom, and Z = 2. Polyanion 1 is composed of two (P4W24O92) fragments that are linked by four equivalent diorganotin groups. The unprecedented assembly 1 has D-2d symmetry and contains a hydrophobic pocket in the center of the molecule. The cyclic voltammetry pattern of 1 is constituted by a first broad, 16-electron reduction wave followed by a second large current intensity wave. No splitting of the first reduction wave could be obtained at moderate scan rate values, even though two well-separated oxidation processes are associated with it. The characteristics of the first wave are clearly different from those obtained for the polyanion precursor [H2P4W24O94](22-) and the related, wheel-shaped [H7P8W48O184](33-), which is due to the {Sn(CH3)(2)} fragments in 1. However, no feature was observed in the voltammogram which could be associated with reduction of the Sn centers.