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Polyacrylonitrile(PAN) fiber was treated with low-temperature plasmas of argon and oxygen for surface modification, and its surface chemical structure and morphology were examined by a field emission scanning electron microscope(FESEM) and a Fourier-transform infrared microspectroscopy(IMS). The argon-plasma treatment caused the only mechanical effect by sputtering of ion bombardment, whereas the oxygen plasma brought about a chemical effect on the PAN fiber surface. The experimental evidences strongly suggested that cyclization of nitrile group and crosslinking were likely to occur in the oxygen-plasma treatment. On the other hand, with the argon-plasma treatment, numerous tiny pits resulted in ranging from several tens to hundreds nanometers in radius. The plasma sensitivity of functional groups such as C-H, C≡N, and O-C=O groups in the PAN fiber was dependent on their chemical nature of bonding in the oxygen-plasma, in which the ester group was the most sensitive to the plasma. Vacuum-ultraviolet(VUV) radiation emitted during plasma treatment played no substantial role to alter the surface morphology.