A　novel　ternary　nanostructure　polyphosphazene　nanotube　(PZS)@　mesoporous　silica　(M-SiO2)@bimetallic　phosphide　(CoCuP)　was　facilely　fabricated,　using　PZS　as　the　template,　where　large　amount　of　cetyltrimethylammonium　bromide　molecules　were　anchored　to　PZS　via　a　similar　layer-by-layer　assembly　strategy,　and　then　uniform　M-SiO2　shells　can　be　formed　successfully　by　Hyeon＇s　coating　method.　Subsequently,　the　three-dimensional　(3D)　nanostructure　on　the　basis　of　bimetallic　phosphide　(CoCuP)　interconnected　with　PZS@M-SiO2　was　synthesized　via　a　convenient,　mild　hydrothermal　route.　It　is　noted　that　incorporating　well-designed　PZS@M-SiO2@CoCuP　led　to　significant　decrease　on　fire　hazard　of　thermoplastic　polyurethane　(TPU),　that　is,　58.2%　and　19.4%　reductions　in　peak　heat　release　rate　and　total　heat　release,　respectively,　as　well　as　lower　toxic　hydrogen　cyanide　and　carbon　monoxide　yield　accompanied　by　higher　graphitized　char　layer.　In　the　case　of　TPU/PZS@M-SiO2@CoCuP　system,　the　storage　modulus　at　-97　°C　was　dramatically　improved　by　62.6%,　and　glass　transition　temperature　was　shifted　to　higher　value,　compared　to　those　of　pure　TPU.　The　enhanced　fire　safety　and　mechanical　property　for　TPU　composites　can　be　ascribed　to　tripartite　cooperative　effect　from　respective　parts　(CoCuP　and　M-SiO2)　plus　the　PZS.　©　2017　American　Chemical　Society.