The rapid growth of electronic devices, including wearable sensors, has increased electronic waste, driving interest in sustainable, biocompatible materials. Electrospun biomaterials have emerged as versatile substrates for multifunctional wearable textiles, offering flexibility, high surface area, tunable porosity, and biocompatibility. Using natural polymers (e.g., silk fibroin, cellulose, chitosan) and synthetic polymers (e.g., polycaprolactone, polylactic acid, PVDF), electrospinning produces nanofibrous mats capable of supporting thermal regulation, moisture management, and integrated sensing for pressure, temperature, humidity, or chemical detection. Nature-inspired designs, hybrid composites, and advanced architectures enable passive and active thermoregulation via phase-change materials, thermochromic dyes, hydrogels, and conductive nanofibers, while maintaining wearer comfort, breathability, and skin safety. Despite progress, challenges persist in durability, washability, energy efficiency, manufacturing scalability, and recyclability. This review provides a comprehensive overview of biomaterials, fabrication techniques, multifunctional sensor integration, and thermoregulation strategies, highlighting opportunities for next-generation wearable textiles that combine sustainability, adaptive thermal management, and high-performance sensing.