Micro/nanostructures can increase effective surface area and enhance the performance of wearable devices, such as the sensitivity of sensors and output of triboelectric nanogenerators. Empowering commercial fibers and fabrics with durable and robust micro/nanostructures has become a major research concern for sustainable wearables. Many technologies are developed to fabricate micron/nanostructures on fibers and textiles, such as breath figure method, electrospinning, and direct imprinting thermal drawing. However, most of these methods have their own limitations toward mass production and real‐life application, including poor solvent resistance, time assuming, requiring expensive equipment, and limited capacity for post‐adjustment of commercial textiles. Here, a plasma‐enhanced breath figure (PEBF) technique to fabricate solvent‐tolerant microporous structure on existing fabrics with tailored pore size is developed. By combining the wearable nature of fabrics and the surface engineering power of PEBF, the fabricated solvent‐tolerant microporous fabric offers excellent flexibility, washability, breathability, and suitability for large‐scale production, as well as the advantages of cost effectiveness and fast production. Furthermore, wearable triboelectric nanogenerators based on solvent‐resistant microporous structured fabrics, revealing the bright future of the PEBF technology in wearable devices and smart textiles are fabricated.