A high-performance triboelectric nanogenerator (TENG) has been developed for breath sensing applications, utilizing tribopositive electrospun nylon-6 nanofibers and tribonegative fluorinated ethylene propylene (FEP). The optimization toward the development of electrospun nylon-6-based TENG includes a range of factors such as the applied force and frequency on tribo responses, the thickness of the fiber mat, the concentration of nylon-6 in the fiber mats, and the selection of the tribonegative material for pairing with nylon-6 nanofiber. Among these parameters, the nanofiber prepared with 18 wt% nylon-6, characterized by a uniform fiber distribution, the highest surface area of 55.69 m2 g−1, and an optimal thickness of 0.169 mm, demonstrated excellent TENG performance, among others. The TENG module constructed using nanofiber in a 4 cm2 area showed the TENG responses of more than 30 μA short-circuit current, 200 V open-circuit voltage, and 90 nC charge when hand-pressed. It achieved a substantial power density of 890 mW m−2 at 20 MΩ by applying a constant force of 10 N at a 10 Hz frequency. Charging a 1 μF capacitor to approximately 30.1 V in just 30 s highlights the potential of electrospun nylon-6 as a promising material for nanogenerator energy harvesting and sensing applications. The TENG device was found to be sufficient to power small, portable electronics such as LEDs and digital watch displays. A wearable belt was fabricated to showcase its breath-sensing capabilities by pairing it with FEP. The microcontroller connected to the TENG in the wearable belt is used to analyze the output produced through breathing patterns, subsequently activating a buzzer and LED by the nature of the breathing.