In the realm of smart textiles, an area garnering significant research attention and demonstrating vast developmental potential, we have conceived and fabricated a multifunctional smart textile with a fire dual-warning function. This innovation integrates thermoelectric performance, triboelectric nanogenerator (TENG), flame retardancy, and hydrophobic functionalities into a cohesive entity. Employing a straightforward impregnation method, we successfully infused cotton fabric (CF) with a novel flame retardant (named AA). Additionally, CF/PPA is modified by incorporating poly(3,4-ethylene dioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS) and polydimethylsiloxane (PDMS) as separate layers, with the former providing thermoelectric properties and the latter enabling TENG functionality in smart textiles. This configuration exhibits excellent voltage output performance, generating a thermoelectric effect of 221 mV under a temperature differential of 76 K and achieving voltage output as high as 138 V at a vertical contact-separation frequency of 5 Hz. The superior dual-warning function, flame-retardant properties, and hydrophobicity of CF/PPA can be integrated into firefighting apparel, thereby establishing fire-alarm systems with remote signal transmission capabilities to enhance personnel safety. Furthermore, CF/PPA holds promising dual warning application prospects in the field of wearable flame-retardant and fire-alarm systems, thus paving new avenues for the utilization of smart textiles in the realm of the Internet of Things (IoT).