The effects of electrospinning parameters in a wider range on the morphology and diameters of polyacrylonitrile (PAN) fibers are studied in detail. The fibers' diameter increases from 288 to 3469 nm swiftly with the increasing PAN concentration. With the increasing voltage or prolonging gap distance, the diameter increases primarily and decreases later. The combined effects of surface tension, splitting and stretching, electric force, viscosity, and solvent volatilization are the main reasons. Ultrasonic etching method, Atomic force microscope (AFM), Scanning electron microscope (SEM) and X-ray diffraction (XRD) technology have been utilized to verify the nature structure of electrospun PAN fibers. Combining all the results, it is deduced that there are many grooves arranging nearly perpendicular to the fiber axis on the surface of electrospun PAN fibers. The thickness of relative ordered region is 40 to 190 nm and the thickness of amorphous region is 20 to 35 nm.