As contagious bio‐aerosols continue to impact our society, we examine how the morphological traits of large‐scale (15 cm × 93 cm), uniformly thick, electrospun nylon membranes can contribute to the ongoing development of diagnostic, sensor driven, face masks for capturing exhaled breath content. In our study, we compare the capture efficiencies of three types of large‐scale Nylon‐6 nanofiber membranes against those of commercial control textiles for capturing in‐lab simulated salt breath aerosols. Furthermore, samples from the Nylon membranes were grafted with acrylic acid to determine the effects of membrane functionalization on capture efficiency. All nongrafted electrospun Nylon membranes captured 39% to 50% more salinated aerosol than the woven and nonwoven controls, despite weighing nearly 20× less. Ultimately, the nanofiber membranes were found to be far more robust during aerosol capture. Although the grafted membranes underperformed compared to the nongrafted ones, they still captured 20% to 40% more aerosol content sized between 3.5 and 6.0 µm (the known size range of exhaled aerosol from typical human saliva) than the woven controls. The fabrication, functionalization, and exhaled aerosol capture of these large‐scale nanofiber membranes underscores the importance of assessing the lifetime, and usability, of electrospun materials before future integration with diagnostic sensing platforms can be successfully achieved. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44759.