It is significant to research on novel materials and devices for alarm and rescue because of catastrophic fire and rainstorm accidents. However, significant challenges remain in terms of dual extreme environments. Here, a carboxylated multi-walled carbon nanotube (C-MWCNT)-driven triple-enhanced triboelectric material (poly(vinylidene fluoride)/C-MWCNT, P/CM5) was constructed by electrospinning, which had the characteristics of flame retardancy, high triboelectricity, and remarkable mechanical property. It possessed ultrafast self-extinguishing (<1 s) due to the inhibition of fluorine-containing radicals induced by PVDF combustion decomposition and the physical barrier effect of the condensed-phase char layer from C-MWCNT. Surprisingly, the tensile strength of P/CM5 was nearly 356.14% of that of the pure PVDF film. Meanwhile, it also had remarkable hydrophobicity (WCA=123°), which ensured proper functioning when wet with water. The open-circuit voltage of the P/CM5-based triboelectric nanogenerator (P/CM5-TENG) at room temperature was nearly 961.45% compared with that of the casting PVDF-TENG because the β-phase induced by C-MWCNT in PVDF was raised to 80.08%. Notably, it simultaneously excelled in triboelectricity at 200 °C, after burning for 30 s, and entire immersion in water. The P/CM5-based self-powered sensor could monitor human motion status or alarm under dual harsh conditions by a wireless Bluetooth system, which is expected to realize smart rescues in disastrous fire and rainy environments.