Aerogel fibers, known for their lightweight and exceptional thermal insulation properties, provide an ideal material solution for fabricating triboelectric nanogenerators (TENGs) for self-powered wearable electronics in extreme environments, such as firefighting gear. However, current aerogel fibers face limitations due to their poor mechanical properties and lack of performance stability under harsh conditions. Herein, a facile strategy for preparing silica/aramid nanofiber (ANF) composite aerogel fibers with interpenetrated dual networks and a silica-dominant component (≈64 wt.%) is demonstrated; the unique structure and composition endow the composite aerogel fibers with high tensile strength (3.4 MPa), low thermal conductivity (0.033 W (m·K)−1), a large specific surface area (587 m2 g−1), and outstanding fire resistance at 95% porosity, combining the best properties of both ANF and silica aerogel. Moreover, the composite aerogel fibers exhibit excellent mechanical flexibility at extremely low temperatures (−196 °C) and maintain structural integrity even when exposed to flame for up to 5 min. Leveraging these exceptional properties, composite aerogel fiber-based TENGs show high electrical output performance before and after combustion (>94% retention). The fabrication strategy offers promising opportunities for modulating the properties and functionalities of aerogel fibers on demand, holding great potential for future applications in wearable smart protective fabrics for extreme environments.