Ultrafine fibers were spun from polyacrylonitrile (PAN) solution in N,N-dimethylformamide using a homemade electrospinning setup. Fibers with diameter ranging from 80 to 340 nm were obtained. Fiber size and fiber size distribution were investigated for various concentration, applied voltage, and tip-to-collector distance using image analysis. The diameters of the electrospun fibers increase when increasing the solution concentration and decrease slightly when increasing the voltage and needle tip-to-collector distance. Porosity and air permeability are vital properties in applications of electrospun nanofibrous structures. In this study, effects of process parameters on the porosity and air permeability of electrospun nanoweb were investigated as well. Results of statistical analysis showed that solution concentration and applied voltage have significant influences on pore diameters. It was concluded that nanofiber diameter played an important role on the diameter of pores formed by the intersections of nanofibers. A more realistic understanding of porosity was obtained and a quantitative relationship between nanoweb parameters and its air permeability was established by regression analysis. Two separate models were constructed for predicting air permeability in relation to process parameters. Optimization of electrospinning process for producing nanoweb with desirable air permeability is well achieved by these models. The models presented in this study are of high importance for their ability to predict the air permeability of PAN nanoweb both by process or structure parameters. (C) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012