The　construction　of　hierarchical　thermoplastic　polyurethane　(TPU)　composites　with　superior　flame　retardant　and　electromagnetic　shielding　capabilities　hold　significant　practical　importance.　In　this　work,　TPU　composites　loaded　with　a　multilayer　core–shell　flame　retardant　(APP@CoAl-LDH@Si)　and　a　modified　conductive　nanofiller　(MWCNT-NH2-PA)　were　firstly　prepared　through　the　melt　blending　method,　acting　as　surface　layer.　Additionally,　multilayered　MXene　films　functionalized　by　bacterial　cellulose　(BC)　and　dopamine　hydrochloride　(DA)　were　fabricated　via　a　facile　and　efficient　vacuum　filtration　approach.　Finally,　a　PBM　film　was　utilized　as　an　intermediate　layer　to　construct　hierarchical　TPU　composites.　The　results　indicated　that　the　introduction　of　10　wt%　APP@CoAl-LDH@Si　hybrid,　the　peak　heat　release　rate,　total　heat　release,　peak　smoke　production　rate,　and　total　smoke　release　of　the　TPU　composites　were　decreased　by　83.0　%,　61.3　%,　48.5　%　and　66.9　%,　respectively,　compared　with　those　of　pure　TPU　due　to　the　free　radicals　capture　effect　of　APP,　and　the　flame-retardant　functions　of　LDH　and　silane.　Moreover,　the　hierarchical　TPU/APP@CoAl-LDH@Si/CP1-PBM　exhibited　excellent　electromagnetic　shielding　performance,　achieving　43.6　dB　in　the　X-band　because　of　multiple　reflection　losses,　interface　polarization　losses,　and　charge　carrier　movement-induced　thermal　dissipation.　Extraordinarily,　the　A　and　R　coefficients　were　reversed　in　the　X　and　K　bands.　This　phenomenon　was　attributed　to　the　different　degrees　of　confinement　of　the　multilayer　structure　to　electromagnetic　waves　with　different　wavelengths.　This　work　presents　a　novel　model　for　the　design　and　preparation　of　high-performance　polymer　composites　with　multiple　properties　and　regulation　mechanism.　©　2025