Potassiumα-andβ-trivanadoenneatungstogermanateswerepreparedandcharacterizedbymeansofelementalanalysis,IR,51Vand183WNMRspectraandpolarography.Thesinglecrystalstructureofa-isomerwasdetermined.ThefinalRis0.083.TheresultsshowthattwopreparedheteropolyanionshaveKegginstructure,anda-isomerbelongstoA-typeandhasstrongeroxidizingabilitythanβ-isomer.