The montmorillonite (MMT) intercalated polyvinyl alcohol (PVA) is used to enhance the triboelectric performance and charge retention ability of the PVA composite film, thereby enhancing the electrical output performance of the PVA-based triboelectric nanogenerator (TENG). The montmorillonite was peeled off under 3 000 r/min high-speed mechanical stirring, then mixed with PVA powder, dissolved at 80 ℃ under mechanical stirring and cast into a film. The blank PVA film was took as a control to test the dielectric constant of the MMT@PVA composite film and the triboelectric charge dissipation curve in the static state to characterize the dielectric and storage properties of the PVA composite film doped with montmorillonite; PVA -PTFE based TENG was used as a control to test the electrical output performance of MMT@PVA-PTFE based TENG to characterize the influence of MMT doping on the triboelectric performance of the PVA composite film. The doping of MMT has a significant effect on the dielectric properties, triboelectricity and charge dissipation of the PVA film. The experimental results show that when 1% of the PVA mass is doped with MMT, the dielectric constant of the PVA composite film is increased by 35%, the charge dissipation rate is reduced by 46%, and the electrical output of the PVA-based TENG is increased by 373%; MMT@PVA-based TENG can light up 868 LEDs and has a stable electrical output. The doping of MMT can significantly improve the triboelectricity and storage properties of PVA film, and help to increase the electrical output of PVA-based TENG, which is significant for broadening the fields of PVA-based TENG in energy harvesting, wearable electronic devices and biosensing.