Due to the ongoing development of portable/mobile electronics, sources to power have received widespread attention. Compared to chemical batteries as power sources, triboelectric nanogenerators (TENGs) possess lots of advantages, including the ability to harvest energy via human motions, flexible structures, environment‐friendliness, and long‐life characteristics. Although many self‐healable TENGs are reported, the achievement of a muscle‐like elasticity and the ability to recover from inevitable damage under extreme conditions (such as a high/low temperature and/or humidity) remain a challenge. Herein, a “double‐terminal aromatic disulfide” on a structure with zwitterions as branched chains is reported to engineer the high‐efficient self‐healable elastomer for application in a flexible TENG. The as‐designed material exhibits a repeatable elastic recovery (at 250% elongation) and a self‐healing efficiency with an ultimate tensile stress of 96% over 2 h, representing an improvement on previously reported disulfide‐based elastomers. The elastomer can autonomously recover by 50% even at a subzero temperature of −30 °C within 24 h. The elastomer‐based TENG, as a self‐driven sensor for detecting human behavior, is demonstrated to exhibit stable outputs and self‐healing in the temperature range of −30 to 60 °C, and so is expected to promote the development of self‐powered electronics for next‐generation human–machine communications. An environmental‐inert and self‐healing triboelectric nanogenerator based on double‐terminal aromatic disulfide bonds and zwitterions not only acts as power generators but also serves as the self‐powered human–machine interface device via harvesting biomechanical energy. Notably, the energy harvester remains the excellent properties at harsh conditions such as subzero regions and the desert.