Sixnewcompounds,α,β-KaHb[GeW9M3(H2O)3O37].xH2O(M=Al,Ga,In;a+b=7)andα-K9H5[Ge2W18Ga6(H2O)3O74].20H2O,weresynthesizedfromthelacunaryprecursorsαandβ-GeW9O3410-andcharacterizedbyelementalanalysis,spectroscopyandelectrochemistry.Tungsten-183NMRspectraofthetitlecomplexesconsistoftwolineswithintensityratio2:1asexpectedfortrisubstitutedheteropolyanions.Theintensityratioofα-Gacompoundis1:2,whichisdifferentfromothers(2:1).WiththehelpofFABmassspectrum,weconcludedthatitisadimerwithD3h,structureinaqueous,andtheothersexistbymonomerswithC3cstructures.