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• Nacre-like GO-PTA paper is prepared by evaporation-induced self-assembly method. • Fire sensor-based GO-PTA exhibits ultrasensitive and durable warning response. • Enhancement in fire resistance of GO is attributed to in situ phosphorus doping. A novel nacre-like flame-retardant paper based on graphene oxide (GO), and phytic acid (PTA) is fabricated via evaporation-induced self-assembly. This facile method is time saving and low energy consuming. A facile approach is proposed to improve thermal oxidative stability of GO paper by in situ phosphorus doping during flame exposure. Then fire-alarm system is designed based on the high-temperature thermal reduction characteristic of GO. The GO paper functionalized with PTA (GO-PTA) can provide ultrasensitive, reliable and longtime fire early-warning signal. Fire alarm can be triggered at approximately 0.50 s when GO-PTA samples are attacked by fire. Phosphorus atoms are in situ doped into graphene layers during fire exposure, endowing GO-PTA paper with outstanding thermal oxidative stability, and thus alarm duration time of GO is greatly improved. The work develops advanced fire detection and early-warning sensors that provide reliable and continuous signals, which provide more available time for fire evacuation. [ABSTRACT FROM AUTHOR]