Electron beam (e-beam) irradiation of polyacrylonitrile (PAN) was performed to investigate the effects of radiation on the electrospinning process. For this study, polyacrylonitrile powder was subjected to e-beam irradiation with different doses of up to 100 kGy under an N-2 atmosphere. Polymer solutions were prepared by dissolving PAN in N,N-dimethyl-formannide (DMF) at a 1:9 ratio by weight. The prepared PAN/DMF solutions showed different colors with different e-beam doses. The resulting structures in solutions contained conjugated C=N bonds, which caused the observed color formation. In addition, the conductivity of the PAN/DMF solution increased with an increase in e-beam irradiation dose. In the DSC spectra of electrospun PAN fibers, the peak temperature of the exothermic reactions was observed to decrease with an increase in the e-beam irradiation strength.