Abstract: Developing triboelectric materials with both high sensitivity and wear comfort is of great significance for advancing the development of self-powered wearable devices. Based on the "internal-external synergy" strategy, this study employs leather (LCF) as the flexible substrate and modifies leather collagen fibers using POSS-based polyionic liquid (POSS-MI) and polyethyleneimine (PEI). This modification synergistically enhances the charge trapping, transfer, and generation capabilities of the leather, thereby constructing a high-sensitivity leather triboelectric sensing material (POSS-MI/LCF@PEI). The results demonstrate that the open-circuit voltage of the proposed leather triboelectric sensing material can reach 266 V, which is 4.03 times higher than that of unmodified leather, and the sensing sensitivity attains 9.08 V*kPa⁻¹ within the range of 5-30 kPa. Meanwhile, the output voltage remains stable after 2000 s of cyclic operation. Additionally, the material not only exhibits excellent antibacterial activity (antibacterial rate > 99%) but also possesses favorable air permeability and water vapor transmission. When utilized as a wearable sensor, it enables real-time monitoring of various human activities, holding broad application prospects in the field of wearable electronics.