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Particulate matter (PM) pollution in the air has become a serious environmental issue that has demanding requirements for the fabrication of new materials. In this study, three different types of nanofiber materials (i.e., cellulose diacetate (CDA), poly(acrylonitrile) (PAN), and poly(vinylidene fluoride) (PVDF)) produced from solution blow spinning were used in composite multilayered filter masks, and their filtration performance for particulate matter of at least 2.5 μm in size (PM2.5) was evaluated. PM2.5 capture efficiency and nanofiber filter pressure drop were tested using the fabricated set-up with simulated burnt cigarette smoke as a source of PM2.5. Filter mask performance using different nanofiber materials was evaluated through their corresponding quality factors (QF). Among the three nanofibers tested, PAN nanofiber has the highest filtration performance with a quality factor of 0.05 Pa–1 and acceptable air permeability. PVDF has the lowest air filter quality among all the nanofibers studied, with a quality factor of 0.02 Pa–1. Insights on the high performance of the nanofiber materials in filter masks are further discussed in this study. Aside from the nanoscale advantage of the nanofibers tested, it is argued that the different molecular functionalities present in the polymeric nanofibers have a significant influence on its filtration performance. In conclusion, all nanofibers used in this study have better filter performances compared to the commercial surgical masks.