Abstract To address the low charge capture capacity and poor wear resistance of triboelectric materials, lithium‐ion intercalation is employed to synthesize monolayer–multilayer hybrid MoS 2 nanosheets. Density functional theory calculations elucidate layer‐dependent charge transfer and band structure modulation in the exfoliated MoS 2 , providing theoretical support for enhanced surface charge capture. By leveraging MoS 2 ’s exceptional charge‐trapping capability and tribological advantages, a MoS 2 /polytetrafluoroethylene (PTFE) composite film exhibiting high negative triboelectric polarity and ultralow friction characteristics is developed. The optimized 2.8 wt.% film exhibits a negative surface potential of −0.31 kV and a coefficient of friction (COF) of 0.07, representing a 416.7% increase in the absolute value of negative surface potential and a 65.5% reduction in COF compared to pure PTFE. The wind‐driven triboelectric nanogenerator (TENG) delivers 452 V, 58 µA, and 6.98 mW at 19.5 m s −1 , maintaining ≈95% of its initial open‐circuit voltage over 21.6 million cycles. A self‐powered heart rate monitor belt and respiratory sensor are fabricated, highlighting its potential for physiological monitoring. This work provides a strategy for triboelectric material design, offering a reference for developing high‐performance and ultra‐durable TENGs.