The　combination　of　polyoxoniobates　(PONbs)　with　3d　metal　ions,　azoles,　and　organoamines　is　a　general　synthetic　procedure　for　making　unprecedented　PONb　metal　complex　cage　materials,　including　discrete　molecular　cages　and　extended　cage　frameworks.　By　this　method,　the　first　two　PONb　metal　complex　cages　K4@{[Cu29(OH)7(H2O)2(en)8(trz)21][Nb24O67(OH)2(H2O)3]4}　and　[Cu(en)2]@{[Cu2(en)2(trz)2]6(Nb68O188)}　have　been　made.　The　former　exhibits　a　huge　tetrahedral　cage　with　more　than　120　metal　centers,　which　is　the　largest　inorganic–organic　hybrid　PONb　known　to　date.　The　later　shows　a　large　cubic　cage,　which　can　act　as　building　blocks　for　cage-based　extended　assembly　to　form　a　3D　cage　framework　{[Cu(en)2]@{[Cu2(trz)2(en)2]6[H10Nb68O188]}}.　These　materials　exhibit　visible-light-driven　photocatalytic　H2　evolution　activity　and　high　vapor　adsorption　capacity.　The　results　hold　promise　for　developing　both　novel　cage　materials　and　largely　unexplored　inorganic–organic　hybrid　PONb　chemistry.　©　2019　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim