AbstractIndustrialization and anthropogenic activities are expected and unavoidable to consummate the current resources of humankind, which also lead to accidents in the laboratory, chemical plants, or other high risk areas that cause severe burns, or even casualties. Increased casualties in such accidents are due to inappropriate safety measures and prevention. Here, a smart anti‐chemical protective suit with a bio‐motion energy harvesting and self‐powered safety monitoring system is demonstrated, which can protect the body from chemical harm, detect sudden chemical spills, monitor human real‐time living signals, and trigger alarms in an emergency. Particularly, a fabric triboelectric nanogenerator (F‐TENG), which is fabricated by the all‐fiber single‐electrode triboelectric nanogenerator yarn (SETY), works as the basic elements of the intelligent suit. The SETY with core‐shell structured design shows a high sensitivity to the corrosive liquids including acids and alkalis. Furthermore, the working principle of the yarn based nanogenerator that is powered by contacting with acid liquid droplets is demonstrated for the first time. In addition, discretionary thickness, permeability, and any other functionalities are also achieved by taking advantage of the fabric structure. This self‐powered smart anti‐chemical protective suit equipped with a real time monitoring system will benefit the wearer who works in a very high‐risk environment.