Understanding of the triboelectric charge accumulation from the view of microcapacitor formation plays a critical role in boosting the output performance of the triboelectric nanogenerator (TENG). Here, an electrospun nanofiber-based TENG (EN-TENG) using a poly(vinylidene fluoride-trifluoroethylene) (PVDF-TrFE)/MXene nanocomposite material with superior dielectric constant and high surface charge density is reported. The influence of dielectric properties on the output performance of the EN-TENG is investigated theoretically and experimentally. The fabricated EN-TENG exhibited a maximum power density of 4.02 W/m2 at a matching external load resistance of 4 MΩ. The PVDF-TrFE/MXene nanocomposite improved the output performance of the EN-TENG fourfold. The EN-TENG successfully powered an electronic stopwatch and thermo-hygrometer by harvesting energy from human finger tapping. Moreover, it was utilized in smart home applications as a self-powered switch for controlling electrical home appliances, including fire alarms, fans, and smart doors. This work presents an effective and innovative approach toward self-powered systems, human-machine interfaces, and smart home applications.