The aim of the present study was to first fabricate an electrospun PVC nanofiber web and then assess its applicability in sampling and measuring the concentration of airborne crystalline silica by comparing analysis results with a commercial PVC membrane filter under different ranges of airborne silica concentration. A filtration performance comparison was also made between an electrospun PVC web with nano-sized fibers and a commercial PVC membrane filter. Overall, the measured concentration of silica by the electrospun webs was 1.022 times higher than that of the commercial PVC filter in all studied ranges of silica concentration and the nanofiber media had higher filtration efficiency and lower pressure drop compared to the PVC membrane filter. This can be considered to be due to the lower fiber diameter and greater porosity (obtained from the 2D SEM image) of the electrospun nanofiber webs. This makes them suited for air pollutant sampling and determining its airborne concentration.