As a clean, sustainable energy source, sound can carry a wealth of information and play a huge role in the Internet of Things era. In recent years, triboelectric acoustic sensors have received increasing attention due to the advantages of self-power supply and high sensitivity. However, the triboelectric charge is susceptible to ambient humidity, which reduces the reliability of the sensor and limits the application scenarios significantly. In this paper, a highly moisture-resistant fluorinated polyimide composited with an amorphous fluoropolymer film was prepared. The charge injection performance, triboelectric performance, and moisture resistance of the composite film were investigated. In addition, we developed a self-powered, highly sensitive, and moisture-resistant porous-structure acoustic sensor based on contact electrification. The detection characteristics of the acoustic sensor are also obtained.