Triboelectric nanogenerators (TENGs) have attracted many researchers’ attention with their remarkable potential despite the fact that the practical implementation requires further improvement in their electric performance. In this work, a novel graphene phase two-dimension material, graphitic carbon nitride (g-C3N4), was employed for the development of a TENG material with enhanced features. An electrospun nanofibrous PA66 membrane doped with g-C3N4 was fabricated as a multifunctional TENG for harvesting different kinds of mechanical energy and detecting human motions. By utilizing the innovative 2D material in PA66 solution for electrospinning, the as-made TENG showed a two times enhancement in electrical performance as compared to the control device, and also had the advantages of lightweight, softness, high porosity, and rugged interface properties. The assembled TENG with 4 cm2 could light up 40 light-emitting diodes by gentle hand clapping and power electronic watches or calculators with charging capacitors. At a given impact force of 40 N and 3 Hz, the as-made TENG can generate an open-circuit voltage of 80 V, short current of ±3 µA, charge transfer of 50 nC, and a maximum power density of 45 mW/m2 at a load resistance of 500 MΩ. The UV light sensitivity of TENG was also improved via g-C3N4 doping, showing that charge transfer is very sensitive with a two times enhancement with dopant. For the demonstration of applications, the g-C3N4 doped TENG was fabricated into an energy flag to scavenge wind energy and sensor devices for detecting human motions.