Ultrafine fibers were electrospun from Polyacrylonitrile and N,N-dimethylformamide solution to be used as a precursor for carbon nanofibers. An electrospinning set-up was used to collect fibers with diameter ranging from 104 nm to 434 nm. Morphology of fibers and its distribution were investigated by varying Berry's number, charge density, spinning angle, spinneret diameter and collector area. A more systematic understanding of process parameters was obtained and a quantitative relationship between electro- spinning parameters and average fiber diameter was established by using response surface methodology. It was concluded that; Berry's number, charge density and spinneret diameters played an important role to the diameter of nanofibers and its standard deviation. Spinning angle and collector area had no sig- nificant impact. Based on response surface methodology the optimum Polyacrylonitrile average fiber diameter of 280 nm and 28 nm standard deviation, were collected at 1.6 kV/cm charge density, 8 Berry's number and 0.9 mm spinneret diameter.