The functionality and use of wearable triboelectric nanogenerators (TENGs) are significantly impacted by the development of their tribomaterial properties. Herein, a novel charge-generating layer (CGL) composed of a V2CTx/Silicone nanocomposite and serpentine TENG (S-TENG) is introduced. The V2CTx/Silicone nanocomposite exhibits a highly electronegative surface, which significantly enhances the surface potential and charge density. The fabricated nanocomposite-based TENG exhibits a peak power density of 19.75 W m−2. It also exhibits a high mechanical stretchability (400%), which is significantly better than those of previously reported TENGs under small external pressure. The optimized S-TENG is demonstrated as a self-powered human motion sensor with high sensitivity (4.93 V kPa−1) and a quick rise time (21 ms). Furthermore, a real-life demonstration of sign language interpretation using finger motion detection and text conversion via smartphones is successfully performed. Additionally, the real-time sensing ability of the S-TENG is demonstrated in virtual reality car games controlled by finger touch. The S-TENG is demonstrated to capture different types of human motion energy for continuously powering a stopwatch and wristwatch. Therefore, it is expected that the V2CTx/Silicone nanocomposite will continue with the contributions of novel CGL materials for various TENG applications including wearable self-powered sensors, robotics, and healthcare monitoring in IoT platforms.