All-nanofiber self-powered device was fabricated using simple, low-cost, safe, and scalable solution blow spinning (SBS) technology for real-time respiratory monitor and timely identification of respiratory obstruction clinically. Polytetrafluoroethylene (PTFE) and polyamide-66 (PA66) nanofibers were selected as triboelectric pairs, owing to strong ability to gain electrons of PTFE and supply electrons of PA66. Poly (ethylene oxide) (PEO) was added to regulate spinning solution viscosity and prepare PTFE/PEO nanofibers, and the morphology and diameter distribution of nanofibers were discussed. PTFE nanofiber film was obtained after the decomposition of PEO in PTFE/PEO nanofiber and melt flow of PTFE pellets in a limited region, and possessed a tensile strength of 1.05 MPa and elongation at a break of 288.58%. Later, PTFE/PA66 all-nanofiber self-powered device was constructed containing PA66 nanofibers, and Au deposition film was used as electrodes by magnetron sputtering. The as-obtained device showed robust electrical performance with an open circuit voltage of ~ 110 V at a loading force of 10 N, a short-circuit current of ~ 5 uA at a loading force of 10 N and a frequency of 4 Hz, a maximum power density of 562 mW·m^–2, and a current of 3.1 uA at a loading resistance of 30 MΩ. Based on the triboelectric mechanism, the device possessed stable response and effective sensibility for stimuli, was used to monitor human breathing conditions, prevent suffocation, and distinguish slow, normal, and fast breathing, with an output voltage of ~ 0.08 V perceived in one normal respiratory circle.