The　development　of　high-efficiency　flame-retardant　polymers　with　low　toxic　fumes　during　combustion　remains　a　great　challenge.　In　this　work,　molybdenum　trioxide　(MoO3)　was　loaded　on　titanium　carbide　(Ti3C2Tx)　nanosheets　through　electrostatic　interactions　for　preparing　a　Ti3C2Tx-MoO3　hybrid.　Then　solvent　mixing　and　melt　blending　methods　were　conducted　to　prepare　flame-retardant　thermoplastic　polyurethane　(TPU)　nanocomposites.　The　scanning　electron　microscopy　(SEM)　result　showed　that　the　uniformly　distributed　Ti3C2Tx-MoO3　hybrid　had　a　strong　adhesion　and　good　compatibility　with　the　TPU　matrix.　The　thermal　stability　of　TPU　was　significantly　improved　upon　the　introduction　of　Ti3C2Tx-MoO3.　The　cone　results　revealed　that　the　peak　of　heat　release　rate　and　the　peak　of　smoke　production　rate　of　TPU　nanocomposites　containing　2.0　wt%　Ti3C2Tx-MoO3　were　significantly　reduced　by　26.2%　and　42.9%,　respectively,　as　compared　to　those　of　pure　TPU.　Besides,　the　peak　of　the　carbon　monoxide　production　rate　and　the　total　carbon　monoxide　yield　of　Ti3C2Tx-MoO3-2.0　were　reduced　by　44.7%　and　44.7%,　respectively.　The　distinguished　fire　resistance　of　the　TPU/Ti3C2Tx-MoO3　system　is　principally　attributed　to　the　physical　barrier　effect　and　the　catalytic　carbonization　of　Ti3C2Tx-MoO3　hybrids　together　with　the　chemical　conversion　of　Ti3C2Tx　©　2022　The　Royal　Society　of　Chemistry.