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The first Keggin-type Be-containing heteropolyanion [BeW12O40]6− (16−) has been obtained by hydrothermal synthesis from sodium tungstate and Be(NO3)2. It was crystallized as (Bu4N)4.8Na1.2[BeW12O40] (1a) and (Me2NH2)6[BeW12O40]·4H2O (1b) salts, which were characterized by 9Be and 183W NMR, ESI-MS, CV, and single crystal X-ray diffraction analysis.