The　first　series　of　niobium–tungsten–lanthanide　(Nb-W-Ln)　heterometallic　polyoxometalates　{Ln12W12O36(H2O)24(Nb6O19)12}　(Ln=Y,　La,　Sm,　Eu,　Yb)　have　been　obtained,　which　are　comprised　of　giant　cluster-in-cluster-like　({Ln12W12}-in-{Nb72})　structures　built　from　12　hexaniobate　{Nb6O19}　clusters　gathered　together　by　a　rare　24-nuclearity　sodalite-type　heterometal–oxide　cage　{Ln12W12O36(H2O)24}.　The　Nb-W-Ln　clusters　present　the　largest　multi-metal　polyoxoniobates　and　a　series　of　rare　high-nuclearity　4d-5d-4f　multicomponent　clusters.　Furthermore,　the　giant　Nb-W-Ln　clusters　may　be　isolated　as　discrete　inorganic　alkali　salts　and　can　be　used　as　building　blocks　to　form　high-dimensional　inorganic–organic　hybrid　frameworks.　©　2016　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim