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　K-4@{[Cu-29(OH)(7)(H2O)(2)(en)(8)(trz)(21)][Nb24O67(OH)(2)(H2O)(3)](4)}　and　[Cu(en)(2)]@{[Cu-2(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)]@{[Cu-2(trz)(2)(en)(2)](6)[H10Nb68O188]}}.　These　materials　exhibit　visible-light-driven　photocatalytic　H-2　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.