Industrialization and human activities have introduced numerous hazards, including exposure to harsh chemicals, radiation, static electricity, and fire risks, particularly in high‐risk sectors such as engineering, rescue operations, military, and aerospace. This study presents a multi‐functional protective textile developed from a conductive fiber composed of polytetrafluoroethylene (PTFE) and carbon nanotubes (CNT), crucial for ensuring personal safety. The conductive fiber demonstrates remarkable strength (17.3 MPa), high porosity (76%), and significant electrical conductivity (185 S m−1), coupled with excellent fineness and flexibility due to its dual‐nanofibrous structure. The resulting textile exhibits exceptional hydrophobicity, chemical resistance, and high electromagnetic interference shielding effectiveness (29 dB in the X‐band), alongside a superior UV protective factor (>3000) and anti‐static properties. Notably, it possesses outstanding electro/photo thermal conversion capabilities, enabling consistent heat generation for personal warmth. Additionally, the textile responds electrically to deformation and temperature changes, facilitating intelligent applications such as motion and temperature monitoring and fire alerts. This work offers a novel strategy for fabricating PTFE‐based composite fibers with porous microstructures and high electrical conductivity, setting a new standard for next‐generation protective clothing with advanced functionalities.