Polarizers are widely applied in antiglare glasses, planner displays, photography filters and optical communications, etc. In this investigation, we propose a new strategy for the preparation of a flexible film polarizer based on the electrospinning technique. An aligned assembly of polyvinyl acetate (PVA) nanofibers was electrospun and collected by a fast-rotating drum, then soaked in polymethyl methacrylate (PMMA) solution and dried thoroughly to obtain a transparent PVA-PMMA composite film polarizer. The morphology, structure and optical performance of the PVA nanofibers and the film polarizers were characterized with a scanning electron microscope, UV-vis-IR spectrometer and polarized Raman spectra, etc. The PVA-PMMA film polarizer demonstrated efficient polarizing activity toward visible and near-infrared light, while keeping fair transparency in the range of 400-1400 nm. Due to the protection from the hydrophobic PMMA matrix, the PVA-PMMA film polarizers show high moisture resistance, making it applicable in a humid environment. Considering the scalability and versatility of the strategy employed here, the PVA-PMMA film polarizer prepared could replace the conventional film polarizers in a wide range of applications.