Triboelectric nanogenerators (TENGs) are promising for a variety of applications that require a reliable output performance and stability. In this work, by utilizing the synergistic effect of lithium chloride (LiCl) and MXene, poly(vinyl alcohol) (PVA) based composite films with humidity-sensitive properties were prepared and employed as a friction layer to achieve self-powered TENGs with enhanced output performance under high humidity. The composite material demonstrates exceptional and stable output performance in the humidity range of 30–95% while exhibiting a strong linear correlation with increasing relative humidity (RH). At 95% RH, its short-circuit current increases up to 31.91 μA, which is three times the output of the TENG fabricated by PVA and PTFE (P-TENG). The rich hydroxyl group in PVA, the strong hygroscopicity of LiCl, and the microcapacitor network provided by MXene nanosheets significantly improve the water absorption capacity and surface roughness of the composite material, resulting in an excellent triboelectric output of TENG. Short-circuit current of the TENG in a wide range of RH (from 50% to 98%) responds very sensitively to humidity fluctuations in the environment and superior adsorption–desorption performance as humidity decreases. Furthermore, TENG regarded as a power supply in high humidity conditions was realized and it can light up 240 LEDs instantaneously with the transfer charge density of TENG reaching 194.37 μC m–2. This technology presents an effective method for stable energy harvesting and self-powered sensing in fog, the ocean, and other high-humidity environments.