Polymer nanofibers are widely adopted in energy harvesting and pressure sensing applications owing to the large contact area and inherent compressibility. Herein, a high-performance triboelectric nanogenerator (TENG) based on 2D siloxene-polyvinylidene fluoride (S-PVDF) composite nanofibrous membrane is newly evaluated. Through proper ratio optimization and facile electrospinning, the fabricated membrane shows significant improvement in dielectric property, electronegativity, and compressibility. The TENG comprising S-PVDF membrane and Nylon 6/6 can deliver an excellent power density of 13.25 W m −2 (f ≈ 5 Hz) and easily operates low-power electronics and Internet of things (IoTs). In addition, the excellent compressibility of membrane extends its applicability to self-powered simultaneous detection of dynamic and static pressure, which is investigated by developing a hybrid pressure sensor (HPS) through effective integration of TENG and a capacitive pressure sensor. The HPS shows an excellent dynamic (12.062 V kPa −1 at (<3 kPa) and 2.58 V kPa −1 at (3-25 kPa)) and static (25.07 mV kPa −1 at (<3 kPa) and 5.96 mV kPa −1 at (3-25 kPa)) pressure sensitivities, respectively. Furthermore, a 2 × 2 HPS array tested and analyzed for multiple users using artificial intelligence significantly improves the accuracy (98%). Remarkable energy harvesting performance and greater accuracy of the HPS manifests better preferences for future self-powered IoT and smart tactile-based user authentication systems.