The emerging field of wearable electronics requires power sources that are flexible, lightweight, high-capacity, durable, and comfortable for daily use, which enables extensive use in electronic skins, self-powered sensing, and physiological health monitoring. In this work, we developed the core–shell and biocompatible Cs2InCl5(H2O)@PVDF-HFP nanofibers (CIC@HFP NFs) by one-step electrospinning assisted self-assembly method for triboelectric nanogenerators (TENGs). By adopting lead-free Cs2InCl5(H2O) as an inducer, CIC@HFP NFs exhibited β-phase-enhanced and self-aligned nanocrystals within the uniaxial direction. The interface interaction was further investigated by experimental measurements and molecular dynamics, which revealed that the hydrogen bonds between Cs2InCl5(H2O) and PVDF-HFP induced automatically well-aligned dipoles and stabilized the β-phase in the CIC@HFP NFs. The TENG fabricated using CIC@HFP NFs and nylon-6,6 NFs exhibited significant improvement in output voltage (681 V), output current (53.1 μA) and peak power density (6.94 W m–2), with the highest reported output performance among TENGs based on halide-perovskites. The energy harvesting and self-powered monitoring performance were further substantiated by human motions, showcasing its ability to charge capacitors and effectively operate electronics such as commercial LEDs, stopwatches, and calculators, demonstrating its promising application in biomechanical energy harvesting and self-powered sensing.