Hybrid organic/inorganic Wells-Dawson polyoxcitungstates have been prepared through addition of functionalized tricholorostannanes to lacunary α 2- and α(1)-[P2W17O61](10-). Coupling of amines and alcohols to polyoxotungstate platforms led to new structures in good yields. Coupling of chiral amines to the previously unknown organotin-substituted a, derivatives allowed the isolation of diastereomers, which feature in some cases split H-1, C-13, and P-31 NMR spectra. This is the first example of NMR observation of a single pair of diastereomers in the α(1)-Wells-Dawson series. It opens the way to potential resolution of those chiral polyoxotungstates.