Triboelectric nanogenerators (TENGs) are emerging as a sustainable and environmentally friendly approach for energy harvesting and self-powered sensing, because of their diverse material options, simple structure, and efficient energy conversion. However, developing tribopositive materials with both high-charge-inducing and high-charge-trapping capabilities remains a significant challenge. Herein, a high-performance TENG is developed based on a polyaniline (PANI) embedded polyacrylonitrile (PAN) nanofiber membrane (NM) (P/P NM) for energy harvesting and self-powered wireless sensing. The incorporation of PANI significantly enhanced the electrical performance, mechanical properties, and thermal stability of P/P NMs. The P/P NM-based TENG achieved an output voltage of 726 V, a short-circuit current density of 32 μA/cm2, and a peak power density of 23.3 W/m2, which were approximately 2.3, 3.6, and 4.6 times higher than those of the pristine PAN NM-based TENG, respectively. Detailed investigations revealed that the embedded PANI improved the electron-donating ability and dielectric constant (by 4.25 times) of P/P NMs, thereby significantly boosting the electrical output of the TENG. The mechanical energy harvesting ability was elucidated through capacitor charging and the operation of low-power devices. Furthermore, the P/P NM-based TENG was integrated into a self-powered wireless sensing system, which enabled the cross-scale monitoring of human signals ranging from tiny pulses to large-scale movements. The introduction of PANI nanofillers provides a simple, effective, and scalable strategy for developing high-performance positive tribomaterials, thus, advancing the practical application of TENGs in energy harvesting and self-powered sensing.