A　series　containing　the　highest　nuclearity　polyoxoniobate　(PONb)　nanoclusters,　ranging　from　dimers　to　tetramers,　has　been　obtained.　They　include　one　114-nuclear　{Li-8　subset　of　Nb114O316},　one　81-nuclear　{Li3K　subset　of　Nb81O225},　and　one　52-nuclear　{H4Nb52O150}.　The　Nb　nuclearity　of　these　PONbs　is　remarkably　larger　than　those　of　all　known　high-nuclearity　PONbs　(＜=　32).　Furthermore,　the　introduction　of　3d　Cu2+　ions　can　lead　to　the　generation　of　extended　inorganic-organic　hybrid　frameworks　built　from　novel,　high-nuclearity,　nanoscale　heterometallic　PONb　building　blocks　{H3Cu3Nb78O222}　or　{H3Cu4(en)Nb78O222}.　These　building　blocks　also　contain　the　largest　number　of　Nb　centers　of　any　heterometallic　PONbs　reported　to　date.　The　synthesis　of　new-type　PONbs　has　long　been　a　challenging　subject　in　PONb　chemistry.