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In order to obtain F-III fibers with high mechanical properties, pristine F-III fibers were hot drawn at the temperature of 250 °C, pressure of 14 MPa, tension of 6 g·d^−1, and different times, which were 15 min, 30 min, 45 min, 60 min, 75 min, 90 min, and 105 min, respectively, in supercritical carbon dioxide (Sc-CO₂) in this article. All the samples, including the pristine and treated F-III fibers, were characterized by a mechanical performance tester, wide-angle X-ray scattering (WAXS), small-angle X-ray scattering (SAXS), and thermogravimetric analysis (TGA). The results showed that the thermal stability of F-III fibers was enhanced to some extent, and the tensile strength and modulus of F-III fibers had great changes as the extension of treatment time during hot drawing in Sc-CO₂, although the treatment temperature was lower than the glass transition temperature (Tg) of F-III fibers. Accordingly, the phase fraction, orientation factor f_c of the (110) crystal plane, fibril length l_f, and misorientation angle B_φ of all the samples were also investigated. Fortunately, the hot drawing in Sc-CO₂ was successfully applied to the preparation of F-III fibers with high mechanical properties.