In this study, the oxyfluorination of PAN-based carbon fibers was undertaken at room temperature using fluorine-oxygen mixtures, and the influence of oxyfluorination on properties was investigated. The surface characteristics of the modified fiber were determined by using X-ray photoelectron spectroscopy (XPS) and dynamic contact angle analyzer. The oxyfluorination of carbon fibers was one of the more effective methods to increase surface wettability by the formation of semicovalent C-F bond and C-O bond depending on reaction conditions. When oxygen mole fraction is increased from 0.5 to 0.9, it is probable that attached fluorine atoms at the surface of the fibers reacted with other components. As increased oxyfluorination time and decreased its pressures, semi-covalent peak is increased at 0.5 of oxygen mole fraction. The total surface free energy of oxyfluorinated carbon fibers decreased with increasing oxygen mole fraction over 0.5. These results indicate that the surface of carbon fibers became much more hydrophilic after the short oxyfluorination. The surface free energy of oxyfluorinated carbon fibers progressively decreased after 10 min treatment. The polar components of surface free energies were however, significantly higher for all oxyfluorinated samples than that for the untreated carbon fiber.