Electrospinning is an efficient method to produce polymer fibers with a diameter range from nanometers to a few microns using an electrically driven jet. Electrospun nanofiber nonwoven fabrics can be applied into different areas with higher air volume fraction, especially applied into textile materials with good warmth retention property. In this article, the air volume fraction in nonwoven mats made of electrospun nanofibers was verified by studying fiber volume fraction in the mats. Then the relationship between fiber volume fraction and fiber diameter was derived, and the fiber volume fraction is in direct ratio to the square of fiber radius. By experimental verification, to get electrospun PAN nanofiber nonwoven mats with high air volume fraction about 99 %, it can fix the polymer concentration on 8 %. The voltage fixed on 20 kV, the tip-to-collector distance on 15 cm. The experiment is in accordance with the theory excellently.