A　rare　3D　porous　inorganic-organic　polyoxoniobate　framework　based　on　the　cubic　polyoxoniobate-cupric-complex　cage　{[Cu(en)2]@{[Cu2(en)2(trz)2]6(Nb68O188)}}　(1a),　has　been　successfully　synthesized　by　a　hydrothermal　method.　The　cubic　cages　1a　are　connected　with　4-(tetrazol-5-yl)pyridine　to　form　a　1D　pillar-like　chain　structure,　and　every　1D　pillar-like　chain　is　further　linked　with　four　adjacent　pillar-like　chains　by　the　[Cu(en)2]2+　complex　to　form　a　3D　porous　inorganic-organic　polyoxoniobate　framework　with　4-connected　CdSO4-type　topology.　To　our　knowledge,　it　is　the　first　time　that　three　different　types　of　organic　ligands　are　simultaneously　introduced　into　one　polyoxoniobate.　This　material　also　exhibits　a　high　vapor　adsorption　capacity　and　good　ionic　conductivity　properties.　©　2020　American　Chemical　Society.