The use of a high-performance and low-cost electrospun nanofiber membrane to remove harmful pollutants from the air is highly valuable in terms of commercial applications. In this paper three functional materials were successfully fabricated into a low-cost, high-performance fibrous mat via a simple and one-step electrospinning technology. These materials included coal fly ash (CFA), which is an industrial waste mainly derived from coal-fired power plants with an adsorption capacity for adsorbing of volatile organic compounds (VOCs); silver nitrate (AgNO3), which imparts excellent antibacterial ability; and polyacrylonitrile (PAN), which serves as an electrospun substrate with high spin-ability. The binding properties of different amounts of CFA powder, AgNO3 and PAN were observed and analyzed in detail by field emission scanning electron microscopy (FE-SEM), biological transmission electron microscopy (Bio-TEM), X-ray diffraction (XRD) and other experimental analyses. The results show that the PAN nanofibers containing 40 wt% CFA (relative to the weight of PAN) had the highest VOCs adsorption capacity compared with other membranes. Furthermore, 2 wt% AgNO3 (relative to the weight of PAN) and 40 wt% CFA powder can be easily fabricated with and PAN nanofibers, and this electrospun PAN/CFA/AgNO3 composite membrane has excellent antibacterial ability on Gram-negative Escherichia coll. (E. coli) (ATCC 52922) and Gram-positive Staphylococcus aureus (S. aureus) (ATCC 29231) bacteria. These electrospun fibrous mats currently stand as an emerging material that has huge development potential for treatment of environmental pollutants.