In this study, the Taguchi method with orthogonal array design was employed to modify polyacrylonitrile (PAN) fabric to endow the material with superhydrophilic performance. FT-IR and XPS analyses proved that after individual treatment of NaOH or H2O2, cyclization/mild-hydrolysis or cyclization/dehydrogenation occurred on the surface of PAN with slight hydrophilic improvement. Only under the synergy of NaOH@H(2)O(2)mixed system, did the obtained PAN fabric show superhydrophilicity, ascribed to the production of abundant hydrophilic groups (-CONH2 and-COONa) on PAN fibers. Meanwhile, the modified PAN fabric presented enhanced mechanical and thermal stability, and could effectively separate various oil/water mixtures with separation efficiency beyond 99.9% and have a high oil intrusion pressure after wetted by water. The rectified performance of PAN fabric made the material a potential candidate for water purification.