Single-use face masks pose a threat to the environment and are not cost-effective, which prompts the need for developing reusable masks. In this study, pressurized gyration (PG) successfully produced bead-on-string polyvinylidene fluoride (PVDF) fibers with fiber diameters ranging from 2.3 μm to 26.1 μm, and bead diameters ranging from 60.9 μm to 88.5 μm by changing the solution parameters. The effect of the solution parameters on the crystalline phase was studied by Fourier-transform infrared spectroscopy (FT-IR), where the β-phase contents of PG PVDF fibers reached over 75%. The fiber morphology and β-phase contents of PG PVDF fibers indicated the potential mechanical and electrostatic filtration efficiency of PG PVDF fibers, respectively. Additionally, the hydrophobicity was investigated by static water contact angle tests, and the PVDF fibers showed superior hydrophobicity properties (all samples above 125°) over commercial polypropylene (PP) single-use masks (approximately 107°). This study supports the notion that the PG PVDF fiber mats are a promising candidate for future reusable face masks.