As the world marches into the era of the Internet of Things (IoT), the practice of human health care is on the cusp of a revolution, driven by an unprecedented level of personalization enabled by a variety of wearable bioelectronics. A sustainable and wearable energy solution is highly desirable and remains a challenge. Here, we report a high-performance wearable electricity generation approach by manipulating the relative permittivity of a triboelectric nanogenerator (TENG). A compatible active carbon (AC)-doped polyvinylidene fluoride (AC@PVDF) composite film was invented with high relative permittivity and a specific surface area for wearable biomechanical energy harvesting. Compared with the pure PVDF, the 0.8% AC@PVDF film-based TENG obtained an enhancement in voltage, current, and power by 2.5, 3.5, and 9.8 times, respectively. This work reports a stable, cost-effective, and scalable approach to improve the performance of the triboelectric nanogenerator for wearable biomechanical energy harvesting, thus rendering a sustainable and pervasive energy solution for on-body electronics.