Chemical resistant textiles are vital for safeguarding humans against chemical hazards in various settings, such as industrial production, chemical accidents, laboratory activities, and road transportation. However, the ideal integration of chemical resistance, thermal and moisture management, and wearer condition monitoring in conventional chemically protective textiles remains challenging. Herein, the design, manufacturing, and use of stretchable hierarchical core–shell yarns (HCSYs) for integrated chemical resistance, moisture regulation, and smart sensing textiles are demonstrated. These yarns contain helically elastic spandex, wrapped silver-plated nylon, and surface-structured polytetrafluoroethylene (PTFE) yarns and are designed and manufactured based on a scalable fabrication process. In addition to their ideal chemical resistance performance, HCSYs can function as multifunctional stretchable electronics for real-time human motion monitoring and as the basic element of intelligent textiles. Furthermore, a desirable dynamic thermoregulation function is achieved by exploiting the fabric structure with stretching modulation. Our HCSYs may provide prospective opportunities for the future development of smart protective textiles with high durability, flexibility, and scalability.

• The multi-functional textiles with hierarchical core–shell structure are manufactured by large-scale fabrication processes.

• It can prevent the human body from chemical hazards within any stretch range of protective clothing.

• It can work as highly multifunctional stretchable electronics for real-time human motion monitoring.

• It can achieve desirable dynamic thermoregulation function by taking advantage of the fabric structure with stretch modulation.