Generally, the term pollution is derived from the production and consumption of resources, where the produced streams are very wasteful in their current state. Most of these waste streams cannot be reintegrated into the environment efficiently or economically. Air pollution resulting from ambient pollutants such as particulate matter, volatile organic matter, and/or gaseous contaminants represents one of the key environmental concerns of this century. There are many technologies developed for effectively treating air pollutants. However, the science and engineering area that is responsible for tomorrow’s breakthroughs is membrane-based technology. Membrane is one of the promising technologies for air filtration due to its high efficiency, little cost, and simplicity of scale-up. Concerning the outstanding properties of high surface area, enormously porous structure, adaptable pore size and controllable morphology of electrospinning nanofiber membranes, it was an exceptional air-filter candidate. However, despite its exceptional characteristics, the main weakness of nanofibrous membranes are their poor mechanical properties during various applications, especially the separation processes. To overcome this limitation, electrospinning technology can offer an efficient one-step methodology to produce functionalized structures including core-shell and multilayered structures. Moreover, the incorporation of nanofillers onto the different electrospun nanofibers polymeric matrices can easily achieved using electrospinning technology to improve the mechanical and reactive characteristics of the composite fabricated nanofiber membranes. So, this chapter will highlight the manipulation of nanofibrous membrane materials for controlling the air filtration performances of nanofibrous membranes either fabricated using single or blended polymeric matrices. The role of nanomaterials addition to the modification of nanofibrous membrane properties toward air filtration applications will be focused on. Finally, a comprehensive overview of the basic principles of the air pollutant separation mechanisms onto the nanofibrous membranes will be discussed.