Smart　fire　alarm　sensor(FAS)materials　with　mechanically　robust,excellent　flame　retardancy　as　well　as　ultra-sensitive　temperature-responsive　capabil-ity　are　highly　attractive　platforms　for　fire　safety　applica-tion.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　over-come　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　obtain-ing　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～2.3　and～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～1200℃flame　attack),ultra-fast　fire　alarm　response　time(～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.