The　combination　of　electromagnetic　interference　(EMI)　shielding　performance　and　flame-retardant　property　is　essential　for　applications　in　the　field　of　electronics　and　electrics.　To　date,　there　have　been　few　successful　cases　in　achieving　such　portfolios,　due　to　the　different　mechanisms　and　even　mutual　exclusivity　of　these　two　attributes.　Herein,　an　ammonium　polyphosphate@chitosan@carbon　nanotube　(APP@CS@MWCNT)　core-multishell　hybrid　was　synthesized　by　microencapsulation　technology.　Then,　the　hybrid　was　introduced　into　TPU　matrix　to　fabricate　TPU　composites,　acting　as　surface　layer.　Meanwhile,　MXene　film　was　used　as　intermediate　layer　to　construct　hierarchical　TPU　composites.　The　obtained　results　showed　that　after　introduction　of　1　wt%　APP@CS@MWCNT　hybrid,　the　peak　of　heat　release　rate　(PHRR)　and　the　peak　of　smoke　produce　rate　(PSPR)　of　TPU　composites　decreased　by　67.4%　and　35.6%,　respectively,　compared　with　those　of　pure　TPU.　Owing　to　multiple　reflection　losses,　interface　polarization　losses,　and　charge　carrier　movement-induced　thermal　dissipation,　TPU/15AC@4M−SW　exhibited　the　highest　EMI　shielding　performance,　and　obtained　shielding　effectiveness　values　of　35.7　dB　and　38.9　dB　in　X　band　and　K　band,　respectively.　©　2023　Elsevier　Inc.