The ongoing global pandemic has bestowed high priority uponthe separation of air-borne particulate matters (PMs), aerosols, etc. using nonwoven fibrous materials, especially for face masks as a means of personal protection. Although spunbond or meltblown nonwoven materials are amongst the forerunners for polymer microfiber-based face mask or air filter development in mass scale, relatively new process of nonwoven manufacturing such as electrospinning is gaining a lot of momentum amongst the filter membrane manufacturers for its scalability of nanofiber-based filter membrane fabrication. There are several nanofiber-based face masks developing industries, which claim a very high efficiency in filtration of particulate matters (PM0.1–10) as well as other aerosols for their products. Polyvinylidene fluoride (PVDF), which is commonly known for its use of tactile sensors and energy harvesters, due to its piezoelectric property, is slowly gaining popularity among researchers and developers as an air filter material. Electrospun PVDF nanofibers can be as fine as 50 nm in mass scale, which allows the membrane to have large surface area compared to its volume, enhancing nanofiber–PM interaction. At the same time, the breathability index can be improved through these PVDF nanofiber membranes due to their architectural uniqueness that promotes slip flow around the fibers. The conductive nature of PVDF makes it advantageous as a promising electret filter allowing better capturing of ultrafine particles. This review aims to provide a comprehensive overview of such PVDF nanofiber-based filter membranes and their roles in air filtration, especially its application in filtrate of air-borne PMs.