Nanofiber mats have received considerable attention from researchers in the field of particulate protection. In thisstudy, polyvinylidene fluoride (PVDF) nanofiber mats were prepared on a large scale by a solution blowing process, and thencrosslinked by ultraviolet (UV)-radiation using trimethylolpropane tri-acrylate (TMPTA) as a crosslinker. The structure,morphology, mechanical and thermal properties, and protective performance of the nanofiber mats were evaluated. Resultsshow that the addition of TMPTA and UV treatment decreased the diameter of the nanofibers and enhanced the mechanicalproperties, air permeability, and moisture permeability. Nanofiber mats show higher filtration and lower filtration resistancecompared with a commercial product. Furthermore, the nanofiber mats were bonded with Nylon 6 fabric, which showedgood performance as a novel functional layer in protective clothing.