Smart　fire　alarm　sensor　(FAS)　materials　with　mechanically　robust,　excellent　flame　retardancy　as　well　as　ultra-sensitive　temperature-responsive　capability　are　highly　attractive　platforms　for　fire　safety　application.　However,　most　reported　FAS　materials　can　hardly　provide　sensitive,　continuous　and　reliable　alarm　signal　output　due　to　their　undesirable　temperature-responsive,　flame-resistant　and　mechanical　performances.　To　overcome　these　hurdles,　herein,　we　utilize　the　multi-amino　molecule,　named　HCPA,　that　can　serve　as　triple-roles　including　cross-linker,　fire　retardant　and　reducing　agent　for　decorating　graphene　oxide　(GO)　sheets　and　obtaining　the　GO/HCPA　hybrid　networks.　Benefiting　from　the　formation　of　multi-interactions　in　hybrid　network,　the　optimized　GO/HCPA　network　exhibits　significant　increment　in　mechanical　strength,　e.g.,　tensile　strength　and　toughness　increase　of　similar　to　2.3　and　similar　to　5.7　times,　respectively,　compared　to　the　control　one.　More　importantly,　based　on　P　and　N　doping　and　promoting　thermal　reduction　effect　on　GO　network,　the　excellent　flame　retardancy　(withstanding　similar　to　1200　degrees　C　flame　attack),　ultra-fast　fire　alarm　response　time　(similar　to　0.6　s)　and　ultra-long　alarming　period　(＞　600　s)　are　obtained,　representing　the　best　comprehensive　performance　of　GO-based　FAS　counterparts.　Furthermore,　based　on　GO/HCPA　network,　the　fireproof　coating　is　constructed　and　applied　in　polymer　foam　and　exhibited　exceptional　fire　shielding　performance.　This　work　provides　a　new　idea　for　designing　and　fabricating　desirable　FAS　materials　and　fireproof　coatings.