The development of highly capable soft electronic devices with exceptional attributes, including ultra-stretchability, robustness, and swift self-healing, is of great significance. However, achieving extreme stretchability at the same time as superior self-healing of energy generators remains a formidable challenge. Prevailing strategies aimed at enhancing stretchability and self-healing have predominantly focused on polymer backbone engineering. To address this challenge, we introduced fluoro-based organic small molecules (3N5F) into the polymer matrix, creating π-πF stacking and fluorine–hydrogen bonds with the polymer chains. The weak interactions formed between the sliding crosslinkers (3N5F molecules) and the polymer chains result in materials with ultra-stretchability (surpassing 20,000% strain without rupture) and rapid self-healing ability (recovering 100% of the mechanical properties within only 1 h). In the pursuit of an ultra-stretchable, self-healing, and conductive composite, we employed liquid metal or carbon black (CB) as conducting fillers for stretchable conductors. These conductors are utilized for motion and position sensing as well as for energy-harvesting triboelectric nanogenerators (TENGs). These show consistent performance, signifying a substantial advancement in the realm of next-generation self-powered electronics designed for the detection of human movement.