A tin(IV) oxoalkoxo cluster with unprecedented architecture,has been prepared and characterized by single-crystal X-ray diffraction. The cluster obeys the formula Sn12O8(OH)(4)(OEt)(28)(HOEt)(4) (1) and is based on an elongated centrosymmetric assembly of 12 six-coordinate tin centers, 28 peripheral ethoxy groups (terminal and bridging), 8 oxo bridges (mu(2) and mu(3)) hydroxy bridges (mu(2)), and 4 ethanol molecules that are all bound to tin atoms and interact strongly, through hydrogen bonds, with an ethoxy group located on a vicinal tin atom. This compound has also been fully characterized in solution by multinuclear 1D and 2D NMR, with all of its Sn-119, H-1, and C-13 NMR resonances assigned with respect to the structure. Altogether, the data allowed unambiguous location of the hydroxy groups. Information on the exchange of the ethoxy groups is also presented.