An　abundance　of　early　warning　graphene-based　nano-materials　and　sensors　have　been　developed　to　avoid　and　prevent　the　critical　fire　risk　of　combustible　materials.　However,　there　are　still　some　limitations　that　should　be　addressed,　such　as　the　black　color,　high-cost　and　single　fire　warning　response　of　graphene-based　fire　warning　materials.　Herein,　we　report　an　unexpected　montmorillonite　(MMT)-based　intelligent　fire　warning　materials　that　have　excellent　fire　cyclic　warning　performance　and　reliable　flame　retardancy.　Combining　phenyltriethoxysilane　(PTES)　molecules,　poly(p-phenylene　benzobisoxazole)　nanofiber　(PBONF),　and　layers　of　MMT　to　form　a　silane　crosslinked　3D　nanonetwork　system,　the　homologous　PTES　decorated　MMT-PBONF　nanocomposites　are　designed　and　fabricated　via　a　sol-gel　process　and　low　temperature　self-assembly　method.　The　optimized　nanocomposite　paper　shows　good　mechanical　flexibility　(good　recovery　after　kneading　or　bending　process),　high　tensile　strength　of-81　MPa　and　good　water　resistance.　Furthermore,　the　nanocomposite　paper　exhibits　high-temperature　flame　resistance　(almost　unchanged　structure　and　size　after　120　s　combustion),　sensitive　flame　alarm　response　(-0.3　s　response　once　exposure　onto　a　flame),　cyclic　fire　warning　performance　(＞40　cycles),　and　adaptability　to　complex　fire　situations　(several　fire　attack　and　evacuation　scenarios),　showing　promising　applications　for　monitoring　the　critical　fire　risk　of　combustible　materials.　Therefore,　this　work　paves　a　rational　way　for　design　and　fabrication　of　MMT-based　smart　fire　warning　materials　that　combine　excellent　flame　shielding　and　sensitive　fire　alarm　functions.