Graphene　oxide　(GO)-based　intelligent　fire　alarm　sensor　(FAS)　has　recently　been　a　sought-after　research　topic　in　fire　prevention　fields.　However,　it　remains　a　challenge　to　facilely　construct　GO-based　composite　that　simultaneously　possess　mechanical　flexibility,　excellent　flame　resistance,　highly-sensitive　temperature-responsive　behavior,　rapid　fire　response　and　ultra-long　fire　alarming　durability.　Here,　a　nacre-like　ternary　hybrid　paper　is　conveniently　obtained　by　integrating　GO　with　hexachlorophosphazene-based　multi‑hydroxyl　molecule　(HHACP)　and　tannic　acid　(TA)　via　a　facile　and　eco-friendly　water　evaporation-induced　self-assembly　method.　The　resultant　composite　paper　(TA-GO/HHACP)　exhibits　mechanically　flexible　property　with　tensile　strength　of　103.7　MPa　and　toughness　of　1.51　MJ/m3,　comparable　to　2.52　and　5.39　times　higher　than　those　of　pure　GO　paper.　Further,　the　TA-GO/HHACP　paper　displays　excellent　nonflammability　and　high-temperature　resistance　that　can　withstand　continuous　butane　flame　attack　(∼　1200　°C),　resulting　in　ultra-long　sustained　alarming　period　of　＞　1600　s　under　an　open　fire.　More　importantly,　benefiting　from　its　rapid　electrical　resistance　reduction　capability,　such　TA-GO/HHACP　paper　demonstrates　ultra-fast　fire-triggered　response　time　of　∼　0.6　s,　and　ultra-sensitive　early　fire　alarm　responses　to　abnormal　high　temperatures　during　pre-combustion　process,　e.g.,　∼　1　s　at　250　°C　and　∼　19　s　at　200　°C,　respectively,　outperforming　the　best　reported　GO‑based　FAS　counterparts.　This　work　provides　an　inventive　paradigm　to　develop　high-performance　GO-based　intelligent　materials　with　reliable　and　sensitive　early　fire-warning　function.　©　2024　Elsevier　B.V.